TWI519844B - Wettable silicone hydrogel contact lenses - Google Patents

Description

Wettable polyoxygen hydrogel contact lens

The present disclosure is directed to polyoxyxahydrogel contact lenses and related compositions and methods.

The present application claims the benefit of priority to U.S. Provisional Patent Application No. 61/447,176, filed on Jan. 28, 2011, which is hereby incorporated by reference.

Commercially and clinically, polyoxyl hydrogel contact lenses are popular alternatives to hydrogel contact lenses (ie, hydrogel contact lenses that do not contain polyoxymethylene or polyoxylium). It is believed that the presence of oxoxane in the polyoxygenated hydrogel contact lens formulation can affect the properties of the polyoxyl hydrogel contact lenses obtained therefrom. For example, it is believed that the presence of a decane component in a contact lens results in a relatively high oxygen permeability compared to conventional hydrogel contact lenses that do not contain a decane component. In addition, it is believed that the presence of a polyoxyxene component increases the likelihood of the presence of a hydrophobic domain on the surface of the lens of the polyoxyxahydrogel contact lens as compared to conventional hydrogel contact lenses that do not contain a polyoxyxene component. The first generation of polyoxyl hydrogel contact lenses can provide a large amount of oxygen even if the wettability of the lens tends to be lower than desired. A variety of techniques have been developed to overcome the hydrophobicity of the surface of polyoxygen hydrogel contact lenses. Based on the popularity of polyoxygenated hydrogel contact lenses, there is still a need in the art for ophthalmically compatible new polyoxyxahydrogel contact lenses, such as new polyoxyl hydrogels having an ophthalmically acceptable wettable surface. Contact lenses.

Some documents describing polyoxyl hydrogel contact lenses include: US Each of the entire disclosures of which is hereby incorporated by reference in its entirety in its entirety in its entirety in the the the the the the the the the the the the the the the the the the the the the the the the the the the the the the the the the the the the the the the the the the

It has been discovered that the miscible polymerizable composition can be prepared using a combination of a siloxane monomer having a specific structure and a plurality of one or more hydrophilic monomers. These polymerizable compositions may optionally include other oxirane monomers, as well as other polymerizable and non-polymerizable components. The miscible polymerizable compositions produce lenses having ophthalmically acceptable wettable surfaces when used in the preparation of polyoxyxahydrogel contact lenses.

The present disclosure relates to neopolyoxyhydrogel contact lenses. In accordance with the present disclosure, a polyoxyxahydrogel contact lens comprises a polymeric lens body. Polymerized lens main system The reaction product of the polymerizable composition. The polymerizable composition comprises a plurality of lens forming components to provide a polymeric lens body upon polymerization of the composition.

In one example, the present disclosure is directed to a miscible polymerizable composition for use in producing the polyoxyxahydrogel contact lenses of the present invention. The polymerizable composition comprises a first oxoxane monomer represented by the formula (1): Wherein m in the formula (1) represents an integer of 3 to 10, and n in the formula (1) represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each of R ² in the formula (1) is independently a hydrogen atom or a methyl group, wherein the first siloxane monomer has a number average molecular weight of from 400 to 700 Daltons. The polymerizable composition also comprises a second oxoxane monomer having a number average molecular weight greater than 7,000 Daltons. The total amount of the oxoxane monomer present in the polymerizable composition (ie, the total unit of the first oxoxane monomer, the second oxane monomer, and, if present, any other oxane monomer) The number is from 30 unit parts by weight to 50 unit parts by weight. In addition to the two or more oxoxane monomers, the polymerizable composition also comprises at least one hydrophilic guanamine monomer having one N-vinyl group (i.e., a vinyl guanamine monomer). The at least one hydrophilic monomer may comprise a single hydrophilic guanamine monomer having one N-vinyl group, or a combination of two or more hydrophilic vinyl guanamine monomers comprising a hydrophilic vinyl guanamine monomer component . The hydrophilic vinyl guanamine monomer component can comprise a first hydrophilic vinyl guanamine monomer and a second hydrophilic vinyl guanamine monomer. The hydrophilic vinylguanamine monomer or monomer component is present in the polymerizable composition in an amount of from 30 to 60 unit parts by weight. The ingredients in the polymerizable composition are present in an amount such that upon polymerization and hydration, the polymerizable composition produces a polyoxyxahydrogel contact lens having an ophthalmically acceptable wettable lens surface.

The polymerizable composition may also optionally comprise at least one crosslinking agent. The polymerizable composition may also optionally comprise at least one polymerizable component or non-polymerizable component. Optionally, in the polymerizable composition described herein, the first oxane monomer and the second oxane monomer may be present in a ratio of from about 2:1 to about 10:1 (based on unit parts by weight). In the polymeric composition. The polymerizable composition comprising the above first oxoxane monomer and second oxoxane monomer and at least one hydrophilic vinyl guanamine monomer may further comprise an optional third oxane monomer or alternatively to One less crosslinker. The components of the polymerizable composition of the present invention may be miscible even if a large amount of at least one hydrophilic vinyl amide monomer and a high amount of a siloxane monomer are present in the composition. Since the first and second oxoxane monomers are highly miscible with the hydrophilic vinyl guanamine monomer or monomer component, it is not necessary to add a non-reactive organic diluent or dilution to the polymerizable composition. The component, but the polymerizable composition may optionally include one or more organic diluents. Examples of the organic diluent include alcohols such as n-propanol or isopropanol. Additionally, as illustrated in the examples, the polymerizable composition can be further substantially free of N,N-dimethyl acrylamide (DMA), or can be free of DMA.

In another example, the present disclosure is also directed to a polyoxyxahydrogel contact lens comprising a polymeric lens body that is the reaction product of a polymerizable composition. The polymerizable composition comprises a first oxoxane monomer represented by the formula (1): Wherein m in the formula (1) represents an integer of 3 to 10, and n in the formula (1) represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each of R ² in the formula (1) is independently a hydrogen atom or a methyl group, wherein the first siloxane monomer has a number average molecular weight of from 400 to 700 Daltons. The polymerizable composition also comprises a second oxoxane monomer having a number average molecular weight greater than 7,000 Daltons. The total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts by weight to 50 unit parts by weight. The polymerizable composition also comprises at least one hydrophilic vinylguanamine monomer present in the polymerizable composition in an amount of from 30 to 60 unit parts by weight. The polymerizable composition may also optionally comprise a third oxane monomer, or at least one crosslinking agent, or at least one polymerizable or non-polymerizable component, or any combination thereof. Optionally, in the polymerizable composition described herein, the first oxane monomer and the second oxane monomer may be present in a polymerizable ratio of from about 2:1 to about 10:1 (based on unit parts). In the composition. The polymerizable composition can be substantially free of organic diluents, DMA, or both organic diluents and DMA.

Unlike many of the previously described polyoxyl hydrogel contact lenses, when the polymerizable composition used to form the lens does not contain a wetting agent, or when the polymerizable composition used to form the lens does not contain an organic diluent, Or when the lens does not contain a wetting agent, or when the polymeric lens body is washed in a liquid that does not contain a volatile organic solvent, or when the lens is not surface treated or surface modified, or any combination thereof, as described herein The contact lens of the polymeric lens body of the reaction product of the polymerizable composition can have an ophthalmically acceptable wettable lens surface. For example, when the polymerizable composition used to form the lens does not contain an internal wetting agent, or when the polymerizable composition used to form the lens does not contain an organic diluent, or during manufacture, the lens is only free of volatiles The contact lens can have an ophthalmically acceptable wettable lens surface when the liquid of the organic solvent is contacted, or when the lens is not surface treated with plasma, or any combination thereof. In one example, a contact lens having ophthalmically acceptable wettability can be understood as a contact lens having a bubble-catching dynamic advancing contact angle of less than 70 degrees when the contact lens is fully hydrated.

The amount of the component in the polymerizable composition may be such that the resulting polyoxyxahydrogel contact lens has an equilibrium water content (EWC) of 30% wt/wt to 70% wt/wt when fully hydrated, or is completely Hydration with less than 90 degrees The bubble advances the contact angle, or both.

At least one hydrophilic vinyl guanamine monomer of the polymerizable composition of the present invention is understood to comprise or consist essentially of or consist essentially of a hydrophilic guanamine monomer having an N-vinyl group. The hydrophilic vinyl guanamine monomer may comprise or consist essentially of or consist of N-vinyl-N-methylacetamide (VMA).

The at least one hydrophilic vinyl guanamine monomer of the polymerizable composition may be present in the polymerizable composition as a single hydrophilic vinyl guanamine monomer, or may comprise the hydrophilicity of two or more hydrophilic vinyl guanamine monomers The vinyl guanamine monomer component form is present, for example, as a first hydrophilic vinyl guanamine monomer or monomer component and a second hydrophilic vinyl guanamine monomer or monomer component. The polymerizable composition may optionally further comprise or consist of a combination of a single hydrophilic vinyl-containing ether monomer or a hydrophilic vinyl-containing ether monomer.

As previously described, the polymerizable composition further comprises a second oxetane monomer. The second oxane single system has a number average molecular weight of at least 7,000 Daltons of a decane monomer. The second oxane monomer can be a polyfunctional siloxane monomer.

The polymerizable composition comprises only the first oxane monomer and the second oxane monomer, or comprises a first siloxane monomer, a second siloxane monomer, and at least one third siloxane monomer The total amount of the oxoxane monomer present in the polymerizable composition (i.e., the first siloxane monomer, the second siloxane monomer, and, if present, the third or more oxane singles) The total unit weight part of the body) may be from about 30 unit parts by weight to about 50 unit parts by weight, such as from about 35 to about 40 unit parts by weight, from about 33 unit parts by weight to about 45 unit parts by weight, or From about 35 unit parts by weight to about 40 unit parts by weight.

In one example, the second oxoxane monomer can be a oxoxane monomer represented by formula (2): Wherein R ₁ is selected from hydrogen or methyl; R ₂ is selected from hydrogen or C _1-4 hydrocarbyl; m represents an integer from 0 to 10; n represents an integer from 4 to 100; and a and b represent an integer of 1 or greater. ; a+b is equal to 20 to 500; b/(a+b) is equal to 0.01 to 0.22; and the configuration of the oxoxane unit includes a random configuration. In one example of the alkane of formula (2), m is 0, n is an integer from 5 to 10, a is an integer from 65 to 90, b is an integer from 1 to 10, and R ₁ is a base.

When the polymerizable composition comprises a third siloxane monomer, the third oxane monomer may be a siloxane monomer represented by formula (3): Wherein R ³ is selected from hydrogen or methyl; m represents an integer from 0 to 10; and n represents an integer from 1 to 500. In one example of the alkane of formula (3), R ³ is methyl, m is 0, and n is an integer from 40 to 60.

The present disclosure is also directed to a batch of polyoxyxahydrogel contact lenses comprising a plurality of contact lenses formed from a self-polymerizing lens body, the polymeric lens primary system reaction product of the polymerizable composition described herein. In one example, based on the average of the values measured for at least 20 individual lenses in the batch Value, the batch of polyoxyhydrogel contact lenses may have an average equilibrium water content (EWC) of 30% wt/wt to 70% wt/wt, or an average oxygen permeability of at least 55 barrer, or about 0.2 MPa to An average tensile modulus of about 0.9 MPa, or an average bubble trapping dynamic contact angle of less than 90 degrees, or an average bubble trapping static contact angle of less than 70 degrees, or any combination thereof.

The present disclosure is also directed to a method of making a polyoxyxahydrogel contact lens. The method of manufacture comprises the steps of providing a miscible polymerizable composition comprising (a) a first oxoxane monomer represented by formula (1): Wherein m in the formula (1) represents an integer of 3 to 10, and n in the formula (1) represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each of R ² in formula (1) is independently a hydrogen atom or a methyl group, the first oxane has a number average molecular weight of from 400 to 700 Daltons; (b) a second oxane single a body having a number average molecular weight greater than 7,000 Daltons; wherein the total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts by weight to 50 unit parts by weight; and (c) having one a mixture of a N-vinyl hydrophilic guanamine monomer or a vinyl guanamine monomer in an amount of 30 to 60 unit parts by weight in a polymerizable composition; a polymerizable composition in a contact lens mold assembly Polymerizing to form a polymeric lens body; contacting the polymeric lens body with the washing liquid to remove the extractable material from the polymeric lens body; and hydrating the polymeric lens body to form a polyoxyxahydrogel contact lens; wherein the polyoxygenated water gel Glue contact lenses have an ophthalmically acceptable wettable lens surface when fully hydrated. Optionally, in the polymerizable composition, the first oxoxane monomer and the second oxoxane monomer may be present in the polymerizable composition in a ratio of from about 2:1 to about 10:1 (based on unit parts by weight). in. The polymerizable composition can be substantially free of organic diluents, DMA, or both organic diluents and DMA. The method can further comprise packaging the polymeric lens body or the polyoxyxahydrogel contact lens in a contact lens packaging solution in a contact lens package. In one example of the method, when the polymerizable composition used to form the polymeric lens body does not contain a wetting agent, or when the polymerizable composition used to form the polymeric lens body does not contain an organic diluent, or is in polymerization When the lens body does not contain a wetting agent, or when the polymeric lens body is washed in a liquid that does not contain a volatile organic solvent, or when the polymeric lens body is not subjected to surface plasma treatment, or in a polyoxygenated hydrogel contact lens The contact lens of the method is ophthalmically acceptable when it contains a wetting agent physically trapped therein, or when the polyoxygenated hydrogel contact lens does not contain a wetting agent bonded to its surface, or any combination thereof Accept the wettable lens surface. In one example, a contact lens having ophthalmically acceptable wettability can be understood as a contact lens having a bubble-catching dynamic advancing contact angle of less than 70 degrees when the contact lens is fully hydrated.

In one example, the polymerizing step of the method can comprise polymerizing the polymerizable composition in a contact lens mold assembly to form a polymeric lens body having a molded surface formed from a non-polar thermoplastic polymer. In another example, the polymerizing step of the method can comprise polymerizing the polymerizable composition in a contact lens mold assembly to form a polymeric lens body having a molded surface formed from a polar thermoplastic polymer.

In one example, the contacting step of the method can comprise contacting the polymeric lens body with a wash liquor comprising at least one volatile organic solvent. In another example, the contacting step of the method can comprise contacting the polymeric lens body with a wash liquid that is free of volatile organic solvents. In one particular example, the polymeric lens body and the polyoxyxahydrogel contact lens comprising the polymeric lens body are not contacted with a liquid comprising a volatile organic solvent during manufacture.

In one example, the method can further comprise the step of autoclaving the contact lens package to sterilize the polyoxyxahydrogel contact lens and the contact lens packaging solution.

In any of the foregoing polymerizable compositions, or polymeric lens bodies, or polyoxyhydrogel contact lenses, or multi-batch polyoxyhydrogel contact lenses or methods of making contact lenses, the first The oxane monomer may be represented by the formula (1), wherein m in the formula (1) is 4, n in the formula (1) is ¹ , and R ¹ is a butyl group in the formula (1), and the formula (1) Each of R ^{2 is} independently a hydrogen atom or a methyl group, wherein the first siloxane monomer has a number average molecular weight of from 400 to 700 Daltons. The second oxane coefficient has an average molecular weight of at least 7,000 Daltons of a oxoxane monomer. The second oxoxane monomer of the polymerizable composition may be a siloxane monomer having more than one polymerizable functional group, that is, a polyfunctional siloxane monomer, such as a difunctional siloxane monomer or a trifunctional oxirane. Alkane monomer and the like. In a particular example, the optional second oxoxane monomer can be a oxoxane monomer having more than one functional group and having a number average molecular weight of at least 7,000 Daltons. Further examples of optional second oxanes are set forth below. The optional at least one crosslinking agent of the polymerizable composition can comprise a vinyl-containing crosslinking agent. For example, the optional at least one crosslinking agent can be comprised of a vinyl-containing crosslinking agent (ie, all of the non-cerium crosslinking agent present in the polymerizable composition is a vinyl-containing crosslinking agent). Additionally, the optional at least one crosslinking agent can be a crosslinking agent comprising at least one vinyl-containing crosslinking agent and at least one acrylate-containing crosslinking agent. Optionally, in the polymerizable composition, the first oxoxane monomer and the second oxoxane monomer may be present in the polymerizable composition in a ratio of from about 2:1 to about 10:1 (based on unit parts by weight). in. The polymerizable composition can be substantially free of organic diluents, DMA, or both organic diluents and DMA.

Other embodiments of the polymerizable composition, polymeric lens body, lenses of the present invention, lens products, multi-batch lenses, and methods of making contact lenses are set forth in the following description, Examples 1-25, and the scope of the patent application. Each of the features described herein, and each combination of two or more of the features, and each combination of one or more of the defined ranges are included in the present disclosure. Within the scope of the invention, the premise is that the features included in the combination are not mutually contradictory. In addition, any embodiment of the invention may in particular not include any feature or combination of features or any value of the defined range.

As described herein, it has been discovered that a polyoxyxahydrogel contact lens can be formed from a polymerizable composition comprising: a first oxoxane monomer of formula (1), wherein m in formula (1) represents An integer of 3 to 10, wherein n in the formula (1) represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms, and each of the formula (1) One R ^{2 is} independently a hydrogen atom or a methyl group, the first oxane has a number average molecular weight of from 400 to 700 Daltons; (b) a second oxane monomer having more than 7,000 Daltons a number average molecular weight; wherein the total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts by weight to 50 unit parts by weight; and (c) a hydrophilic amide having one N-vinyl group A mixture of bulk or vinylguanamine monomers, which is present in the polymerizable composition in an amount of from 30 to 60 unit parts by weight. Although the polymerizable composition and the resulting polyoxyxahydrogel contact lens formed therefrom have a plurality of two or more siloxane oxide monomers and at least one hydrophilic guanamine-free single having one N-vinyl group Body (ie, vinyl guanamine monomer), but it has been found that when the contact lens is fully hydrated, the polyoxyxahydrate contact lens has an ophthalmically acceptable wettable lens surface, for example having less than 70 degrees The bubble capture dynamically advances the lens surface of the contact angle.

The contact lenses of the present invention comprise or consist of a hydrated lens body comprising a polymeric component and a liquid component. The polymeric component comprises two or more siloxane oxide monomers (ie, the first oxirane monomer of formula (1), wherein m in formula (1) represents an integer from 3 to 10, formula (1) Wherein n represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms, and each R ² in the formula (1) is independently a hydrogen atom or a a first oxane having a number average molecular weight of from 400 to 700 Daltons; a second oxane monomer having a number average molecular weight of greater than 7,000 Daltons; and, as the case may be, one or more other hydrazines An oxane monomer; wherein the total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts by weight to 50 unit parts by weight; and one or more of the quinone-free reaction components (ie, one or more hydrophilic groups) A unit of a vinyl guanamine monomer and, as the case may be, other reaction components)). Thus, it will be understood that the polymeric component is the reaction product of a polymerizable composition comprising two or more oxoxane monomers (in the form of the oxirane monomer component of the composition) Or more than one oxoxane monomer), and one or more of the ruthenium-free reaction components comprising at least one hydrophilic guanamine monomer having one N-vinyl group, the hydrophilic vinyl guanamine single system at 30 to 60 units The amount by weight is present in the polymerizable composition. As used herein, a germanium-free reactive component is understood to be a component having a polymerizable double bond as part of its molecular structure, but which does not have a germanium atom in the molecular structure. The composition of the polymerizable composition can be a monomer, a macromonomer, a prepolymer, a polymer, or any combination thereof. In addition to the first oxoxane monomer of formula (1), the polymerizable composition further comprises at least one hydrophilic monomer. Optionally, the polymerizable composition may further comprise a third oxoxane monomer, or at least one crosslinking agent, or a third oxane monomer and at least one crosslinking agent. Optionally, the components of the polymerizable composition may further comprise at least one hydrophobic monomer, or at least one third oxane monomer, or any combination thereof. At least one crosslinking agent, at least one hydrophilic monomer and at least one hydrophobic monomer of the polymerizable composition are understood to be free of ruthenium polymerizable components. As used herein, at least one crosslinking agent is understood to include a single crosslinking agent or a crosslinking agent component comprised of two or more single crosslinking agents. Similarly, at least one hydrophilic monomer is understood to include a single hydrophilic monomer or a hydrophilic monomer component composed of two or more hydrophilic monomers. At least one hydrophobic monomer is understood to comprise a single hydrophobic monomer or a hydrophobic monomer component consisting of two or more hydrophobic monomers. The at least one third oxane monomer may be understood to comprise a single third oxane monomer or a siloxane monomer component consisting of two or more siloxane monomers. Additionally, the polymerizable composition may optionally comprise at least one starter, or at least one organic diluent, or at least one surfactant, or at least one oxygen scavenger, or at least one color former, or at least one UV absorber, or At least one chain transfer agent, or any combination thereof. Optionally, at least one starter, at least one organic diluent, at least one surfactant, at least one oxygen scavenger, at least one color former, at least one UV absorber, or at least one chain transfer agent is understood to be an antimony component And may be a non-polymerizable component or a polymerizable component (ie, a component having a polymerizable functional group as a part of its molecular structure).

The combination of the polymeric component and the liquid component is present as a hydrated lens body which is suitable for placement on the human eye. The hydrated lens body has a generally convex front surface and a generally concave rear surface with an equilibrium water content (EWC) greater than 10% (weight/weight, wt/wt). Thus, a contact lens of the invention is understood to be a soft contact lens, as used herein, to a contact lens that folds upon itself without breaking when fully hydrated.

As understood in the industry, a daily disposable contact lens is a contact lens that has not been worn, and is taken out from a sealed sterilization package (original package) manufactured by a contact lens manufacturer, placed on a person's eyes, and ends at the end of the day. Remove the lens that has been worn by the person and discard it. Typically, lenses for daily disposable contact lenses are worn for a period of 8 to 14 hours and are subsequently discarded after wearing. The disposable lens is not cleaned or exposed to the cleaning solution prior to being placed on the eye because it is sterile prior to opening the package. The daily throwing polyoxygen hydrogel contact lens is a disposable disposable polyoxygen hydrogel contact lens. In contrast, non-daily disposable contact lenses are replaced with disposable lenses that are less frequent per day (eg, weekly, biweekly, or monthly). Non-daily disposable contact lenses are removed from the eye and periodically cleaned with a cleaning solution, or worn continuously without being removed from the eye. The contact lens of the present invention may be a daily disposable contact lens or a non-daily disposable contact lens.

According to the present disclosure, the miscible polymerizable composition of the present disclosure comprises a first oxoxane monomer represented by formula (1): Wherein m in the formula (1) represents an integer of 3 to 10, and n in the formula (1) represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each R ² in the formula (1) is independently a hydrogen atom or a methyl group. In other words, in the single molecule of the oxirane monomer represented by Formula 1, the first R ² in the formula (1) (the R ² closest to the R ¹ terminal group on the left side of the molecule) may be a hydrogen atom or a methyl group. And the second R ² in the formula (1) (the R ² is a part of the methacrylate end group on the right side of the molecule) may also be a hydrogen atom or a methyl group, regardless of the first R in the formula (1) ² Whether it is a hydrogen atom or a methyl group, the first siloxane monomer has a number average molecular weight of from 400 to 700 Daltons. The polymerizable composition also comprises a second oxoxane monomer having a number average molecular weight greater than 7,000 Daltons. The total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts by weight to 50 unit parts by weight. The polymerizable composition also comprises a mixture of a hydrophilic guanamine monomer or a vinyl guanamine monomer having an N-vinyl group, which is present in the polymerizable composition in an amount of from 30 to 60 unit parts by weight. The amount of the component in the polymerizable composition is such that the resulting polyoxyxahydrogel contact lens has an ophthalmically acceptable wettable lens surface upon complete hydration, for example, as less than 70 degrees from when fully hydrated. The surface of the lens that captures the dynamic advance contact angle is confirmed. The polymerizable composition may also comprise an optional third oxane monomer, or alternatively at least one crosslinking agent, or any combination thereof.

In one example, the first oxane monomer and the second oxane monomer can be present in the polymerizable composition in a ratio of at least 1:1 (based on the unit weight parts). Optionally, the first oxane monomer and the second oxane monomer may be present in a ratio of at least 2:1 (based on unit weight parts). The second oxane monomer may have more than one polymerizable functional group (ie, the second oxane monomer may be a polyfunctional siloxane monomer). If the optional second oxane monomer has two polymerizable functional groups (eg, two methacrylate groups), it is a difunctional monomer. If the second oxane monomer has three polymerizable functional groups, it is a trifunctional monomer.

Where the polymerizable composition comprises the first oxoxane monomer of formula (1) and optionally at least one crosslinking agent, the first oxoxane monomer and optionally at least one crosslinking agent can be at least 10:1 The ratio (based on the unit weight parts) is stored in the polymerizable composition. When the at least one crosslinking agent comprises or consists of a vinyl-containing crosslinking agent or crosslinking agent component, the first oxoxane monomer and the at least one vinyl-containing crosslinking agent or crosslinking agent component (ie, The total unit parts of the single vinyl-containing crosslinker or the total unit parts of the individual crosslinker containing the vinyl crosslinker component can be present in the polymerizable ratio of at least 100:1 (based on the unit weight fraction) In the composition. For example, the ratio can be from about 100:1 to about 600:1, or from about 200:1 to about 500:1, or from about 300:1 to about 400:1 (based on unit parts by weight). In one example, the at least one crosslinking agent can comprise at least one vinyl-containing crosslinking agent and at least one methacrylate-containing crosslinking agent. In another example, the at least one crosslinking agent can consist of only one or more vinyl-containing crosslinking agents. In a particular example, the at least one crosslinking agent can comprise or consist of at least one vinyl ether-containing crosslinking agent.

In one example, the lens can comprise a polymeric lens body that is a reaction product of a miscible polymerizable composition, the miscible polymerizable composition comprising (a) a first oxane single represented by formula (1) body: Wherein m in the formula (1) represents an integer of from 3 to 10, wherein n in the formula (1) represents an integer of from 1 to 10, and R1 in the formula (1) is an alkyl group having from 1 to 4 carbon atoms. And each of R2 in the formula (1) is independently a hydrogen atom or a methyl group, and the first siloxane monomer has a number average molecular weight of from 400 to 700 Daltons; (b) a second oxane single a body having a number average molecular weight greater than 7,000 Daltons, wherein the total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts to 50 unit parts; and (c) at least one of a hydrophilic guanamine monomer of N-vinyl group, the hydrophilic guanamine single system being present in the polymerizable composition in an amount of 30 to 60 unit parts; and (d) at least one vinyl crosslinking agent; wherein the invisible The lens has an ophthalmically acceptable wettable lens surface when fully hydrated. Optionally, the polymerizable composition can be substantially free of N,N-dimethyl acrylamide (DMA), or can be substantially free of organic diluents, or both. Also optionally, in this example, the first oxoxane monomer and the second oxane single system are present in the polymerizable composition in a ratio of from about 2:1 to about 10:1 (based on unit parts by weight). , or any combination thereof. In this example, the ophthalmic acceptability of the lens can be confirmed by the lens surface of the polymeric lens having a bubble-catching dynamic advancing contact angle of less than 70 degrees when fully hydrated. The present disclosure is also directed to one or more neopolyoxyhydrogel contact lenses. In accordance with the present disclosure, a polyoxyxahydrogel contact lens comprises a polymeric lens body. The polymeric lens host system is a reaction product of a miscible polymerizable composition or a contact lens formulation. The miscible polymerizable composition for producing the polyoxyxahydrogel contact lens of the present invention comprises the first oxirane monomer represented by the formula (1): Wherein m in the formula (1) represents an integer of 3 to 10, and n in the formula (1) represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each of R ² in the formula (1) is independently a hydrogen atom or a methyl group, and the first siloxane monomer has a number average molecular weight of from 400 to 700 Daltons. The total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts by weight to 50 unit parts by weight. The polymerizable composition also includes at least one hydrophilic vinyl guanamine monomer. At least one hydrophilic vinyl guanamine mono system is present in the polymerizable composition in an amount of from 30 to 60 unit parts by weight.

It has been discovered that a large amount of one or more hydrophilic vinylguanamine monomers can be prepared by using a combination of a first oxane of formula (1) and a second oxoxane monomer having a molecular weight greater than 7,000 Daltons (eg, 30). Up to 60 unit parts of the miscible polymerizable composition. The miscible polymerizable composition of the present disclosure may be substantially free of, or free of, an organic diluent, or N,N-dimethyl acrylamide (DMA), or both. The miscible polymerizable composition of the present disclosure may further comprise a third oxoxane monomer, or may further comprise at least one crosslinking agent, or may further comprise a third oxoxane monomer and at least one crosslinking agent By.

In general, it is difficult to prepare a miscible polymerizable composition having a large amount of hydrophilic monomers, especially when a higher molecular weight polyoxynoxy monomer (for example, a monomer having a number average molecular weight of at least 3,000 Daltons) is present in the composition. . Even when a miscible polymerizable composition having a large amount of hydrophilic monomer is available, the resulting contact lens may have no ophthalmically acceptable surface wettability. Without wishing to be bound by theory, it is believed that especially when the first oxane monomer is combined with a second oxane having a high molecular weight, the structure of the first oxane can result in a larger amount of hydrophilic vinyl amide monomer. a polymer formed by dissolving in a polymerizable composition and from a unit having a high content of a first oxane, a second oxane, and at least one hydrophilic vinyl guanamine monomer present in the polymerizable composition can be used to produce A polymeric lens body having an ophthalmically acceptable wettable lens surface (e.g., a lens surface having a bubble-catching dynamic advancing contact angle of less than 70 degrees when the lens is fully hydrated).

Similarly, it has been observed that the addition of a crosslinking agent to the polymerizable composition used to prepare the polyoxyxahydrogel contact lens generally has a detrimental effect on the wettability of the resulting polyoxyxahydrogel contact lens. When combined with two or more oxoxane monomers, the addition of a crosslinking agent, especially at higher levels, results in a miscible polymerizable composition, but the resulting contact lenses may not have ophthalmically acceptable surface wettability. . Without wishing to be bound by theory, it is believed, in particular, that the first oxane monomer and the high molecular weight second oxane monomer and the high proportion of at least one hydrophilic vinyl amide monomer and at least one crosslinking agent, especially When combined with a vinyl-containing crosslinker, the structure of the first oxane is particularly advantageous for producing an ophthalmically acceptable wettable lens surface (eg, having a bubble-forming dynamic advancing contact angle of less than 70 degrees when the lens is fully hydrated) Polyurethane condensation on the surface of the lens Glue contact lenses.

Examples of the disclosed polymerizable compositions can be miscible upon initial preparation and can be maintained for a period of time sufficient to manufacture contact lenses (e.g., about 2 weeks, or about 1 week, or about 5 days). Miscible. Typically, the miscible polymerizable composition produces a contact lens having ophthalmically acceptable clarity when polymerized and treated as a contact lens.

A method commonly used to increase the miscibility of a oxoxane monomer and a hydrophilic monomer comprises adding an organic diluent to the polymerizable composition for use as an increase between a hydrophilic monomer and a generally more hydrophobic siloxane monomer. A bulking agent, or only a naphthenic monomer having a low molecular weight (eg, a molecular weight of less than 2,500 Daltons). In one example, the use of the first oxane described above allows for the simultaneous inclusion of a high molecular weight second oxane and a plurality of one or more hydrophilic vinyl guanamine monomers in the polymerizable composition of the present disclosure. And although one or more organic diluents may be included in the polymerizable compositions of the invention disclosed herein, such organic diluents are not required to obtain the miscible polymerizable compositions of the present disclosure. In other words, in one example, the polyoxyxahydrogel contact lenses of the present disclosure are formed from a polymerizable composition that does not contain an organic diluent.

In one example, the lens can comprise a polymeric lens body that is a reaction product of a miscible polymerizable composition, the miscible polymerizable composition comprising (a) a first oxane single represented by formula (1) body: Wherein m in the formula (1) represents an integer of 3 to 10, and n in the formula (1) represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each R ² in the formula (1) is independently a hydrogen atom or a methyl group, and the first siloxane monomer has a number average molecular weight of from 400 to 700 Daltons; (b) a second oxime An alkane monomer having a number average molecular weight greater than 7,000 Daltons, wherein the total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts to 50 unit parts; and (c) at least one A hydrophilic guanamine monomer having an N-vinyl group, the hydrophilic guanamine single system being present in the polymerizable composition in an amount of from 30 to 60 unit parts; wherein the polymerizable composition is substantially free of organic diluent and The contact lens has an ophthalmically acceptable wettable lens surface when fully hydrated. Optionally, the polymerizable composition may be substantially free of N,N-dimethyl decylamine (DMA), or the first oxane monomer and the second oxane monomer may be from about 2:1 to about 10 A ratio of :1 (based on unit parts by weight) is present in the polymerizable composition, or any combination thereof. In this example, the ophthalmologic receptivity of the lens can be confirmed by the lens surface of the polymeric lens having a bubble-catching dynamic advancing contact angle of less than 70 degrees when fully hydrated.

As previously described, the first oxoxane monomer may have a molecular weight of from 400 to 700 Daltons. Further details regarding the first oxane monomer can be found in US 20090299022, the entire disclosure of which is incorporated herein by reference. As can be understood from the formula (1), the first siloxane monomer has a single methacrylate polymerizable functional group present on one end of the main chain of the siloxane main monomer.

In an example of the contact lens of the present invention, the first siloxane monomer can be represented by the formula (1), wherein m in the formula (1) is 4, and n in the formula (1) is 1, in the formula (1) R ¹ is a butyl group, and each R ² in the formula (1) is independently a hydrogen atom or a methyl group. An example of such a first oxane monomer is identified herein as Si1 in Examples 1-25.

In one example, the lens can comprise a polymeric lens body that is a reaction product of a miscible polymerizable composition, the miscible polymerizable composition comprising (a) a first oxane single represented by formula (1) body: Wherein m is 4 in the formula (1), n is in the formula (1), R ¹ is a butyl group in the formula (1), and each R ² in the formula (1) is independently a hydrogen atom or a methyl group, a first oxane monomer having a number average molecular weight of from 400 to 700 Daltons; (b) a second oxane monomer having a number average molecular weight of greater than 7,000 Daltons, wherein The total amount of the oxoxane monomer in the polymerizable composition is from 30 unit parts to 50 unit parts; and (c) at least one hydrophilic guanamine monomer having one N-vinyl group, the hydrophilic guanamine single The system is present in the polymerizable composition in an amount from 30 to 60 unit parts; wherein the contact lens has an ophthalmically acceptable wettable lens surface upon complete hydration. Optionally, the polymerizable composition may be substantially free of organic diluent, or may be substantially free of N,N-dimethyl decylamine (DMA), or a first oxane monomer and a second oxane. The monomers can be present in the polymerizable composition in a ratio of from about 2:1 to about 10:1 (based on unit parts by weight), or any combination thereof. In this example, the ophthalmologic receptivity of the lens can be confirmed by the lens surface of the polymeric lens having a bubble-catching dynamic advancing contact angle of less than 70 degrees when fully hydrated.

Molecular weight as used herein is understood to mean the number average molecular weight. The average molecular weight is an ordinary calculation of the molecular weight of individual molecules present in a monomer sample. Mean or average. Since the molar mass of individual molecules in a monomer sample can be slightly different from each other, there can be some degree of dispersibility in the sample. When the oxoxane monomer or any other monomer, macromer, prepolymer or polymer in the polymerizable composition is polydisperse, the term "molecular weight" as used herein means the average number of monomers or components. Molecular weight. As an example, a sample of a oxoxane monomer can have a number average molecular weight of about 15,000 Daltons, but if the sample is polydisperse, the actual molecular weight of the individual monomers present in the sample can be between 12,000 Daltons. Up to 18,000 Daltons.

The number average molecular weight can be an absolute number average molecular weight as determined by proton nuclear magnetic resonance (NMR) end group analysis as understood by those skilled in the art. The molecular weight can also be determined using gel permeation chromatography as understood by those skilled in the art, or can be provided by the supplier of the chemical.

As previously described, the polymerizable composition of the present invention comprises a first siloxane monomer, a second siloxane monomer, and at least one hydrophilic vinyl guanamine monomer, wherein at least one hydrophilic vinyl guanamine mono system It is stored in the polymerizable composition in an amount of from 30 to 60 parts by number. The polymerizable compositions used to prepare the polyoxyxahydrogel contact lenses of the present invention may also include other optional ingredients in addition to those described above. For example, the polymerizable composition can optionally include a third oxane monomer. In this example, it is understood that the third oxane monomer has a different molecular structure, a different molecular weight, or a different molecular structure and a different molecular weight than the first siloxane monomer or the second siloxane monomer. . The optional third oxane monomer may optionally comprise a third oxane monomer component, wherein the third oxane monomer component comprises two or more oxoxane monomers, each of which Both are different from the first oxane monomer and the second siloxane monomer of the polymerizable composition.

The first oxoxane monomer, the second oxane monomer, and, if present, the optional at least one third oxoxane monomer comprising the polymerizable composition of the oxirane monomer component The number and position of any hydrophilic component (eg, ethylene glycol, polyethylene glycol, and the like) in the molecular structure of the siloxane monomer, the first oxane monomer, or the second oxime Each of the alkane monomers, or alternatively at least one third oxoxane monomer, or any combination thereof, can be a hydrophilic siloxane monomer, or a hydrophobic siloxane monomer, or can have a hydrophilic region and Hydrophobic zone.

For example, the second oxane monomer, or alternatively at least one third oxane monomer, or any combination thereof, may contain a hydrophilic component in the main chain of the siloxane molecule, which may be in the oxane One or more side chains of the molecule contain a hydrophilic component, or any combination thereof. For example, the oxoxane monomer can have at least one ethylene glycol unit adjacent to the polymerizable functional group in the backbone of the siloxane molecule. As used herein, adjacent is understood to mean both directly adjacent and only 10 or fewer carbon atoms apart. At least one ethylene glycol unit adjacent to the polymerizable functional group in the main chain of the siloxane molecule may be separated from the polymerizable functional group by a carbon chain of 1-5 units in length (ie, wherein the ethylene glycol unit is bonded to a length of 1) a first carbon in the carbon chain of the -5 unit, and the polymerizable functional group is bonded to the last carbon in the carbon chain of 1-5 units in length, in other words, the ethylene glycol unit and the polymerizable group are not directly adjacent to each other And separated by 1-5 carbon atoms). The oxoxane monomer can have at least one ethylene glycol unit adjacent to a polymerizable functional group present on both ends of the main chain of the siloxane molecule. The oxoxane monomer may have at least one stored in the oxime An ethylene glycol unit in at least one side chain of an alkane molecule. At least one ethylene glycol unit present in at least one side chain of the siloxane molecule may be bonded to a portion of a side chain of a ruthenium atom in the main chain of the siloxane molecule. The oxoxane molecule may have at least one ethylene glycol unit adjacent to a polymerizable functional group present on both ends of the main chain of the siloxane molecule, and at least one B remaining in at least one side chain of the siloxane molecule Both diol units.

In one example, the lens can comprise a polymeric lens body that is a reaction product of a miscible polymerizable composition, the miscible polymerizable composition comprising (a) a first oxane single represented by formula (1) body: Wherein m in the formula (1) represents an integer of 3 to 10, and n in the formula (1) represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each R ² in the formula (1) is independently a hydrogen atom or a methyl group, and the first siloxane monomer has a number average molecular weight of from 400 to 700 Daltons; (b) a second oxime An alkane monomer having a number average molecular weight greater than 7,000 Daltons, the second oxane monomer having at least one ethylene glycol unit adjacent to a polymerizable functional group in the backbone of the siloxane molecule, wherein The total amount of the oxoxane monomer in the polymeric composition is from 30 unit parts to 50 unit parts; and (c) at least one hydrophilic guanamine monomer having one N-vinyl group, the hydrophilic guanamine single system The photopolymerizable composition is present in an amount from 30 to 60 unit parts; wherein the contact lens has an ophthalmically acceptable wettable lens surface upon complete hydration. Optionally, the polymerizable composition may be substantially free of organic diluent, or may be substantially free of N,N-dimethyl decylamine (DMA), or a first oxane monomer and a second oxane. The monomers can be present in the polymerizable composition in a ratio of from about 2:1 to about 10:1 (based on unit parts by weight), or any combination thereof. In this example, the ophthalmologic receptivity of the lens can be confirmed by the lens surface of the polymeric lens having a bubble-catching dynamic advancing contact angle of less than 70 degrees when fully hydrated.

The hydrophilicity or hydrophobicity of the monomer can be determined using conventional techniques (e.g., based on the water solubility of the monomer). For the purposes of this disclosure, a hydrophilic single system is significantly soluble in the monomer in an aqueous solution at room temperature (e.g., about 20-25 °C). For example, a hydrophilic monomer is understood to mean that 50 grams or more of monomer can be significantly completely soluble in 1 liter of water at 20 ° C as determined by standard shake flask methods known to those skilled in the art (ie, single Any monomer that can be dissolved in water at a concentration of at least 5% wt/wt. The hydrophobic single system used herein is a monomer which is significantly insoluble in an aqueous solution at room temperature such that a plurality of separate, discernible phases are present in the aqueous solution, or the aqueous solution is allowed to stand at room temperature. It became cloudy over time and was divided into two distinct phases. By way of example, a hydrophobic monomer is understood to mean any monomer which, at 20 ° C, is substantially insoluble in 1 liter of water (ie, the monomer is dissolved in water at a concentration of less than 5% wt/wt).

The second oxoxane monomer or optionally at least one third methoxyxane monomer of the polymerizable composition may be an acrylate oxirane monomer, in other words, having at least one acrylate polymerizable functional group as its molecule A portion of the structure of a siloxane monomer. In one example, the acrylate-containing oxirane monomer may be a methacrylate oxirane monomer, ie having at least one methacrylate A polymerizable functional group is a oxoxane monomer that is part of its molecular structure.

The second oxoxane monomer or, optionally, at least one third decane oxide may have a coefficient average molecular weight of at least 3,000 Daltons of a oxoxane monomer. In another example, the oxoxane monomer can be a oxoxane monomer having a molecular weight of at least 4,000 Daltons, or at least 7,000 Daltons, or at least 9,000 Daltons, or at least 11,000 Daltons.

The second oxane monomer or alternatively at least one third oxane monomer can be a oxoxane monomer having a molecular weight of less than 20,000 Daltons. In another example, the optional at least one third oxoxane monomer can be less than 15,000 Daltons, or less than 11,000 Daltons, or less than 9,000 Daltons, or less than 7,000 Daltons, or less than 5,000 deuterium oxonane monomers.

The optional at least one third oxoxane monomer can be a oxoxane monomer having a molecular weight of from 3,000 Daltons to 20,000 Daltons. In another example, the oxoxane monomer can be a oxoxane having a molecular weight of from 5,000 to 20,000 Daltons, or from 5,000 to 10,000 Daltons, or from 7,000 to 15,000 Daltons. monomer.

In one example, the optional at least one third decane monomer has more than one functional group and has a number average molecular weight of at least 3,000 Daltons.

The optional at least one third oxoxane monomer may comprise a poly(organosiloxane) monomer or a macromonomer or prepolymer, for example, carbamic acid 3-[indole (trimethyl decyloxy) Methyl propyl] propyl allyl ester, or 3-[indene (trimethyl decyloxy) decyl propyl] propyl vinyl ester, or trimethyl methacrylate alkyl vinyl acetate Ester, or trimethylmethanyl methyl carbonate vinyl ester, or 3-[indolyl (trimethylformamoxy)carbenyl methacrylate] Propyl ester (TRIS), or 3-(methacryloxy-2-hydroxypropoxy)propyl bis(trimethyldecyloxy)methyldecane (SiGMA), or methyl methacrylate (Trimethyl methoxy)carbenyl propyl glyceryl ethyl ester (SiGEMA), or polydimethyl methoxy oxane (MCS-M11) having a monomethacryloxypropyl propyl end, MCR-M07 Or polydimethyl methoxy oxane (mPDMS) having a monomethacryloxypropyl end and a mono-n-butyl end, or any combination thereof. In one example of the polymerizable composition of the present disclosure, the second oxoxane monomer or the optional at least one third oxane may comprise one or more of the first oxanes described herein, wherein The second oxane monomer or alternatively at least one third oxoalkyl group differs from the first oxane present in the polymerizable composition in molecular weight, molecular formula or molecular weight and molecular formula. For example, the second oxane monomer or the optional at least one third oxane monomer can be a oxoxane monomer of formula (1) in combination with the first oxane in the polymerizable composition. The monomers have different molecular weights. In another example, the second oxoxane monomer or the optional at least one third oxane can comprise at least one of the oxiranes disclosed in the following patents: US 2007/0066706, US 2008/0048350, US 3808178 US 4,120, 570, US 4, 136, 550, US 4, 153, 641, US 470 533, US 5, 070, 215, US 5, 998, 498, US 5, 760, 100, US Pat.

In another example of the contact lens of the present invention, the second oxoxane monomer or the optional at least one third oxoxane monomer can be a double-end methacrylate-terminated polydimethyl siloxane. The number average molecular weight is at least 7,000 Daltons, or at least 10,000 Daltons. It will be understood that these oxirane single systems Bifunctional monomer.

As an example of the difunctional oxirane monomer used in the polyoxyxahydrogel contact lens of the present invention, the second oxoxane monomer or the optional at least one third oxane monomer may be represented by the formula (2) representative: Wherein R ₁ in the formula (2) is selected from a hydrogen atom or a methyl group; R ₂ in the formula (2) is selected from a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; and m in the formula (2) represents 0 to An integer of 10; n in the formula (2) represents an integer of 4 to 100; a and b represent an integer of 1 or more; a+b is equal to 20 to 500; b/(a+b) is equal to 0.01 to 0.22; The configuration of the oxane unit includes a random configuration. In an example in which a monooxane single system is a monomer represented by the formula (2), m in the formula (2) is 0, n in the formula (2) is an integer of 5 to 15, and a is 65 to 90. An integer of the formula, b is an integer from 1 to 10, R ₁ in the formula (2) is a methyl group, and R ₂ in the formula (2) is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. An example of the oxirane monomer represented by the formula (2) is abbreviated as Si2 in Examples 1-25. The number average molecular weight of the siloxane monomer represented by the formula (2) may be from about 9,000 Daltons to about 10,000 Daltons. In another example, the molecular weight of the oxoxane monomer represented by formula (2) can range from about 5,000 Daltons to about 10,000 Daltons. It can be understood that the azoxy group represented by the formula (2) has two terminal methacrylate polymerizable functional groups (that is, a methacrylate group present on each end of the molecular chain of the oxirane of the molecule). Bifunctional oxane. Further details regarding this decyl alkane monomer can be found in US 20090234089, which is incorporated herein in its entirety by reference.

As another example of the difunctional oxirane monomer used in the polyoxyxahydrogel contact lens of the present invention, the second oxane monomer or the optional at least one third oxane monomer may be of the formula ( 3) Representative: Wherein R ^{3 is} selected from a hydrogen atom or a methyl group, m in the formula (3) represents an integer of from 0 to 10, and n in the formula (3) represents an integer of from 1 to 500. In one example, the oxime system is a siloxane monomer represented by Formula 3, and R ³ is a methyl group, m in Formula (3) is 0, and n in Formula (3) is a 40. An integer of up to 60.

In another example, the second oxane monomer or the optional at least one third oxane monomer can be a difunctional siloxane monomer represented by formula (4), and in Examples 1-25 Abbreviated as Si3 (from the product code DMS-R18 from Gelest, Morrisville, PA):

In one example, the decane of formula (4) has a number average molecular weight of from about 4,000 to about 4,500 Daltons.

Another example of a oxoxane monomer useful as an optional at least one third oxoxane monomer can include a monofunctional oxirane monomer having at least one urethane linkage, such as by formula ( 5) Representative monofunctional oxirane monomers: Wherein n in the formula (5) is 0-30, or 10-15. In one example, the oxoxane monomer can be a monomer of formula (5) wherein n in formula (5) is 12-13 and has a molecular weight of about 1,500 Daltons. Such monofunctional oxirane monomers are described in US 6,867, 245, which is incorporated herein by reference.

Yet another example of a oxoxane monomer useful as a second oxane monomer or an optional at least one third oxane monomer can include a bifunctional hydrazine having at least two urethane linkages. An oxane monomer, such as a difunctional oxirane monomer represented by formula (6): Wherein n in formula (6) is an integer from about 100 to 150, m in formula (6) is an integer from about 5 to about 15, h is an integer from about 2 to 8, and p is from about 5 to about An integer of 10. Other examples of such difunctional oxyalkylene monomers and methods of preparing the compounds of formula (6) are described in U.S. Patent No. 6,867,245, incorporated herein by reference. In a particular example, the oxoxane monomer can have two urethane linkages and a molecular weight greater than about 5,000 Daltons (eg, a molecular weight greater than about 10,000 Daltons, or a molecular weight greater than about 15,000 Daltons). Difunctional oxirane monomer.

In one example of a contact lens of the present invention, the second oxoxane monomer or, alternatively, the at least one third oxane monomer can have a number average molecular weight of at least 9,000 Daltons, or at least 11,000 Daltons. Number of oxirane monomers The amount average molecular weight can be less than 20,000 Daltons. Thus, in some cases, the second oxane monomer or the optional at least one third oxane monomer may be considered a macromonomer or prepolymer, but it will be referred to herein as a monomer, This is because it forms 1 unit part of the polymer with the other reactive components in the polymerizable composition.

In the polymerizable composition of the present invention from which the polyoxyxahydrogel contact lens of the present invention is derived, the first siloxane monomer and the second siloxane monomer may be present in the following amounts: the first siloxane monomer and The ratio of the second oxane monomer is at least 1:1 (based on unit parts), or at least 2:1 (based on unit parts). For example, the first oxane monomer and the second oxane monomer can be present in the polymerizable composition in a ratio of from about 2:1 to about 10:1 (based on unit parts). In another example, the first oxane monomer and the second oxane monomer can be present in the polymerizable composition in a ratio of from about 3:1 to about 6:1 (based on unit parts). In one example, the first oxane monomer and the second oxane monomer can be present in the polymerizable composition in a ratio of about 4:1 (based on unit parts).

In one example, the lens can comprise a polymeric lens body that is a reaction product of a miscible polymerizable composition, the miscible polymerizable composition comprising (a) a first oxane single represented by formula (1) body: Wherein m in the formula (1) represents an integer of 3 to 10, and n in the formula (1) represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each R ² in the formula (1) is independently a hydrogen atom or a methyl group, and the first siloxane monomer has a number average molecular weight of from 400 to 700 Daltons; (b) a second oxime An alkane monomer having a number average molecular weight greater than 7,000 Daltons, wherein the oxoxane monomer and the second oxane single system are from about 2:1 to about 10:1 (based on unit weight parts) The ratio is present in the polymerizable composition, and the total amount of the oxirane monomer present in the polymerizable composition is from 30 unit parts to 50 unit parts; and (c) at least one has one N-vinyl group a hydrophilic guanamine monomer, the hydrophilic guanamine single system being present in the polymerizable composition in an amount of from 30 to 60 unit parts; wherein the contact lens has an ophthalmically acceptable wettable lens surface when fully hydrated . Optionally, the polymerizable composition may be substantially free of organic diluent, or may be substantially free of N,N-dimethyl decylamine (DMA), or may comprise at least one vinyl-containing crosslinker, or Any combination. In this example, the ophthalmologic receptivity of the lens can be confirmed by the lens surface of the polymeric lens having a bubble-catching dynamic advancing contact angle of less than 70 degrees when fully hydrated.

The total amount of the oxoxane monomer present in the polymerizable composition (e.g., the first oxirane monomer, the optional second oxane monomer, and any other optional components present in the polymerizable composition) The sum of the unit parts of the siloxane monomer may be from about 25 to about 50 unit parts, or from about 35 to about 40 unit parts.

As used herein, "unit parts" is understood to mean unit parts by weight. For example, to prepare a formulation described as comprising a z unit fraction of a oxoxane monomer and a y unit portion of a hydrophilic monomer, the composition can be prepared by combining z gram oxoxane monomer And y grams of hydrophilic monomer to obtain a total of y + z grams of polymerizable composition, or a combination of z ounces of decane and y ounces of hydrophilic monomer to obtain a total of y + z ounces of polymerizable composition, and the like. In the composition further Including other optional ingredients (for example, x unit parts of cross-linking agent), combining x grams of cross-linking agent with z-gram of alkoxysilane monomer and y grams of hydrophilic monomer to obtain a total of x + y + z grams of polymerizable Composition, and so on. Where the composition comprises other optional ingredients comprising a component consisting of two components, for example, a hydrophobic monomer component consisting of a first hydrophobic monomer and a second hydrophobic monomer, in addition to z unit parts a unit of w unit parts of the first hydrophobic monomer and v unit parts of the second hydrophobic monomer, in addition to the oxirane monomer, the y unit part of the hydrophilic monomer, and the x unit part of the crosslinking agent. The total amount is v+w+x+y+z unit parts of the polymerizable composition. It should be understood that the unit parts of the at least one hydrophobic monomer present in the polymerizable composition is the sum of the unit parts of the first hydrophobic monomer and the unit parts of the second hydrophobic monomer, such as in this example. v+w unit parts. Generally, formulations of the polymerizable composition will be comprised of a total amount of from about 90 to about 110 unit parts by weight. When the amounts of the components in the polymerizable composition are recited herein in unit parts, it is understood that the unit parts of the components are based on the total weight of the composition provided in the range of from about 90 to 110 unit parts. Formulations. In one example, the parts by weight may be based on a formulation that provides a total weight of the composition ranging from about 95 to 105 unit parts by weight, or from about 98 to 102 unit parts by weight.

The polymerizable composition of the present disclosure is understood to include a first siloxane monomer, a second siloxane monomer, and at least one hydrophilic vinyl amide monomer, and optionally at least one hydrazine-free hydrophobic monomer, or At least one non-ruthenium crosslinking agent, or any combination thereof. As used herein, at least one hydrophilic vinyl guanamine monomer and at least one cross-linking agent are ruthenium-free chemistries (ie, chemistries whose molecular structure does not include ruthenium atoms) and are therefore different from those present in the polymerizable composition. a siloxane monomer. In one example, the polymerizable composition can comprise at least one hydrophobic monomer, or at least one crosslinking agent, or any combination thereof, as appropriate.

As stated previously, the polymerizable composition of the present disclosure comprises at least one hydrophilic vinyl guanamine monomer. A hydrophilic vinyl guanamine monomer is understood to be a non-polyoxyl polymerizable component having only one polymerizable functional group present in its molecular structure. The polymerizable composition may comprise a single hydrophilic vinyl guanamine monomer, or may comprise two or more hydrophilic vinyl guanamine monomers in the form of a hydrophilic vinyl guanamine monomer component. In addition to the hydrophilic vinyl guanamine monomer, other non-vinylguanamine-free hydrophilic monomers may optionally be included in the polymerizable composition. Non-vinylguanamine-free hydrophilic monomers useful as hydrophilic monomers or hydrophilic monomer components in the polymerizable compositions disclosed herein include, for example, acrylamide-containing monomers, or acrylate-containing monomers, Or an acrylic acid-containing monomer, or a methacrylate-containing monomer, or a methacrylic acid-containing monomer, or any combination thereof. In one example, the non-vinylamine hydrophilic monomer or monomer component can comprise or consist of a methacrylate containing hydrophilic monomer. It should be understood that the vinyl guanamine hydrophilic monomer or hydrophilic monomer component is a ruthenium free monomer.

Examples of the non-vinylamine hydrophilic monomer which may be included in the polymerizable composition of the present invention may include, for example, N,N-dimethyl acrylamide (DMA), or 2-hydroxyethyl acrylate, or 2-hydroxyethyl methacrylate (HEMA), or 2-hydroxypropyl methacrylate, or 2-hydroxybutyl methacrylate (HOB), or 2-hydroxybutyl acrylate, or acrylic acid 4 -hydroxybutyl ester, or glyceryl methacrylate, or 2-hydroxyethyl methacrylamide, or polyethylene glycol monomethacrylate, or methacrylic acid, or acrylic acid, Or any combination thereof.

In one example, the non-vinylamine hydrophilic monomer or hydrophilic monomer component can comprise or consist of a vinyl containing monomer. Examples of hydrophilic vinyl-containing monomers that may be provided in the polymerizable composition include, but are not limited to, N-2-hydroxyethyl vinyl carbamate, or N-vinyl-beta-alanine N-vinyl ester, Or 1,4-butanediol vinyl ether (BVE), or ethylene glycol vinyl ether (EGVE), or diethylene glycol vinyl ether (DEGVE), or any combination thereof.

As previously discussed, the polymerizable compositions of the present disclosure comprise at least one hydrophilic vinyl guanamine monomer or hydrophilic monomer component. The hydrophilic vinyl guanamine monomer or monomer component comprises a hydrophilic guanamine monomer having an N-vinyl group, for example, N-vinylformamide, or N-vinylacetamide, or N-vinyl -N-ethylacetamide, or N-vinylisopropylamine, or N-vinyl-N-methylacetamide (VMA), or N-vinylpyrrolidone (NVP), or N-vinyl caprolactam, or any combination thereof. In one example, the hydrophilic vinyl guanamine monomer or hydrophilic vinyl guanamine monomer component comprises N-vinyl-N-methylacetamide (VMA), or N-vinylpyrrolidone (NVP) , or any combination thereof. In another example, the hydrophilic vinyl guanamine monomer or hydrophilic vinyl guanamine monomer component comprises N-vinyl-N-methylacetamide (VMA). For example, the hydrophilic vinylguanamine monomer or monomer component can comprise or consist of VMA. In a particular example, the hydrophilic vinyl guanamine monomer can be a VMA.

In another example, the non-vinylamine hydrophilic monomer or monomer component can comprise or consist of a vinyl ether containing monomer. Examples of vinyl ether-containing monomers include, but are not limited to, 1,4-butanediol vinyl ether (BVE), or ethylene glycol ethylene Ethyl ether (EGVE), or diethylene glycol vinyl ether (DEGVE), or any combination thereof. In one example, the non-vinylamine hydrophilic monomer component comprises or consists of BVE. In another example, the non-vinylamine hydrophilic monomer component comprises or consists of EGVE. In yet another example, the non-vinylamine hydrophilic monomer component comprises or consists of DEGVE.

In yet another example, the non-vinylamine hydrophilic monomer component can comprise a first non-vinylamine hydrophilic monomer or monomer component and a second non-vinylamine hydrophilic monomer or hydrophilic monomer component. A combination of or consists of. In one example, the first hydrophilic monomer has a different polymerizable functional group than the second hydrophilic monomer. In another example, each monomer of the first hydrophilic monomer has a different polymerizable functional group than the second hydrophilic monomer. In another example, the first hydrophilic monomer has a different polymerizable functional group than each of the second hydrophilic monomer components. In yet another example, each monomer of the first hydrophilic monomer component has a different polymerizable functional group than each of the second hydrophilic monomer components.

As previously discussed, the hydrophilic vinylguanamine monomer or hydrophilic vinylguanamine monomer component is present in the polymerizable composition in an amount from 30 to 60 unit parts of the polymerizable composition. The hydrophilic vinylguanamine monomer or monomer component may be present in the polymerizable composition in an amount of from 40 to 55 unit parts by weight, or from 45 to 50 unit parts by weight. When the hydrophilic vinyl guanamine monomer component in the polymerizable composition comprises a first hydrophilic vinyl guanamine monomer or monomer component and a second hydrophilic vinyl guanamine monomer or monomer component, second The hydrophilic vinylguanamine monomer or monomer component may be present in the polymerizable composition in an amount from 0.1 to 20 unit parts of the polymerizable composition. For example, in the total amount of 30 to 60 unit parts of the hydrophilic vinylguanamine monomer or monomer component present in the polymerizable composition, the first The hydrophilic vinyl guanamine monomer or monomer component may comprise from 29.9 to 40 unit parts, and the second hydrophilic vinyl guanamine monomer or monomer component may comprise from 0.1 to 20 unit parts. In another example, the second hydrophilic vinyl guanamine monomer or monomer component can be present in the polymerizable composition in an amount from 1 to 15 unit parts, or from 2 to 10 unit parts, or from 3 to 7 unit parts. .

As used herein, a vinyl-containing mono-system having a single polymerizable carbon-carbon double bond (ie, a vinyl polymerizable functional group) present in its molecular structure, wherein under free radical polymerization, a vinyl polymerizable function The carbon-carbon double bond in the group is less reactive than the carbon-carbon double bond present in the acrylate or methacrylate polymerizable functional group. In other words, although a carbon-carbon double bond is present in the acrylate group and the methacrylate group as understood herein, a monomer comprising a single acrylate or methacrylate polymerizable group is not considered to be ethylene-containing. Base monomer. Examples of polymerizable groups having a carbon-carbon double bond which is less reactive than a carbon-carbon double bond in an acrylate or methacrylate polymerizable group include vinyl decylamine, vinyl ether, vinyl Ester and allyl ester polymerizable groups. Thus, examples of vinyl-containing monomers useful herein include monomers having a single vinyl guanamine, a single vinyl ether, a single vinyl ester, or a single allyl ester polymerizable group.

Since the contact lenses of the present disclosure are configured to be placed or placed on the cornea of an animal or human eye, they are ophthalmically acceptable contact lenses. Ophthalmically acceptable contact lenses as used herein are understood to mean contact lenses having at least one of a variety of different properties as described below. In a particular example, an ophthalmically acceptable contact lens is understood to be a contact lens having a lens surface having a bubble-promoting dynamic advancing contact angle of less than 70 degrees when the lens is fully hydrated. mirror. Ophthalmically acceptable contact lenses can be formed from ophthalmically acceptable ingredients and packaged in such ingredients such that the lenses are non-cytotoxic and do not release irritating and/or toxic ingredients during wear. An ophthalmically acceptable contact lens may have sufficient clarity for the intended use of the lens optic zone (ie, the portion of the lens that provides vision correction) for a given use of the cornea in contact with the eye, such as a visible light transmittance of at least 80%, or At least 90%, or at least 95%. Ophthalmically acceptable contact lenses can have sufficient mechanical properties to aid lens operation and care over the duration of their life expectancy. For example, the modulus, tensile strength, and elongation may be sufficient to withstand insertion, wear, removal, and conditional cleaning during the life expectancy of the lens. The extent of such suitable properties will vary depending on the life expectancy and use of the lens (eg, one-day disposable, multiple use monthly, etc.). An ophthalmically acceptable contact lens can have an effective or suitable ion flow to substantially inhibit or substantially prevent corneal staining, such as after continuous wear of the lens on the cornea for 8 hours or more, more severe than superficial or moderate corneal staining. Corneal staining. An ophthalmically acceptable contact lens can have a degree of oxygen permeability sufficient to allow oxygen to reach the cornea of the eye wearing the lens in an amount sufficient to maintain long-term corneal health. An ophthalmically acceptable contact lens can be a lens that does not cause significant or excessive corneal edema in the eye of the lens, for example, no more than about 5% or 10% corneal edema after wearing on the cornea of the eye during overnight sleep. An ophthalmically acceptable contact lens can be a lens that allows the lens to move over the cornea of the eye wearing the lens, which movement is sufficient to facilitate the flow of tears between the lens and the eye, in other words, does not cause the lens to interfere with normal lens movement. The force is attached to the eye, and the lens has a sufficiently low degree of movement on the eye to Allow vision correction. An ophthalmically acceptable contact lens can be a lens that allows the lens to be worn on the eye without excessive or significant discomfort and/or irritation and/or pain. An ophthalmically acceptable contact lens can inhibit or substantially prevent deposition of lipids and/or proteins to a lens sufficient for the lens wearer to remove the lens from the deposit. An ophthalmically acceptable contact lens can have at least one water content, or surface wettability, or modulus or design, or any combination thereof, which can effectively promote contact lens wearers to wear at least ophthalmicly in a day. Contact lenses. Ophthalmically compatible wear is understood to mean that the lens wearer produces little or no discomfort when wearing the lens with little or no corneal staining. Conventional clinical methods can be used to determine if contact lenses are ophthalmically acceptable, such as those practiced by an eye care practitioner and as known to those skilled in the art.

In one example of the present disclosure, a contact lens can have an ophthalmically acceptable wettable lens surface. For example, when the polymerizable composition used to form the polymeric lens body does not contain an internal wetting agent, or when the polymerizable composition used to form the polymeric lens body does not contain an organic diluent, or is in water or not The contact lens may have an ophthalmically acceptable wettable lens surface when the polymeric lens body is extracted in an aqueous solution of a volatile organic solvent, or when the polymeric lens body is not surface treated, or any combination thereof.

One method commonly used in the industry to improve the wettability of contact lens surfaces is to apply treatment or modify the lens surface to the lens surface. In accordance with the present disclosure, a polyoxyxahydrogel contact lens can have an ophthalmically acceptable wettable lens surface without surface treatment or surface modification. Surface treatments include, for example, plasma and corona treatment that increase the hydrophilicity of the lens surface. Although the mirror of the present invention is The sheet body is subjected to one or more surface plasma treatments, but upon complete hydration, such treatment is not required to obtain a polyoxyl hydrogel contact lens having an ophthalmically acceptable wettable lens surface. In other words, in one example, the polyoxyxahydrogel contact lenses of the present disclosure may be treated without surface plasma or corona.

Surface modification includes bonding a wetting agent to the surface of the lens, for example, by chemical bonding or another form of chemical interaction to bond a wetting agent, such as a hydrophilic polymer, to at least one lens surface. In some cases, the wetting agent can be bonded to the lens surface and at least a portion of the polymeric matrix of the lens (ie, at least a portion of the lens body) by chemical bonding or another form of chemical interaction. The ophthalmically acceptable wettable lens surface of the present disclosure may have ophthalmically acceptable wettability without the presence of at least a wetting agent (e.g., polymeric or non-polymeric material) bonded to the lens surface. While one or more wetting agents can be incorporated into the lenses of the present invention, such bonding is not required to obtain a polyoxyxahydrogel contact lens having an ophthalmically acceptable wettable lens surface upon complete hydration. Thus, in one example, a lens of the present disclosure can comprise a wetting agent that is bonded to the surface of the lens, for example, a hydrophilic polymer and includes polyvinylpyrrolidone. Alternatively, in another example, the polyoxyxahydrogel contact lenses of the present disclosure may be free of a wetting agent that is bonded to the surface of the lens.

Another method of increasing the wettability of the lens is to physically trap the wetting agent in the lens body or contact lens by, for example, introducing a wetting agent into the lens body as the lens body expands, and then subjecting the lens body The state of lower expansion is restored, thereby trapping a portion of the wetting agent in the lens body. The wetting agent can be permanently captured within the lens body or can be released from the lens over time (eg, during wear). The ophthalmically acceptable wettable lens surface of the present disclosure may have ophthalmically acceptable wettability without the presence of a wetting agent (eg, polymeric material or material that is physically trapped in the lens body after formation of the polymeric lens body) Non-polymeric material). Although one or more wetting agents can be physically trapped in the lenses of the present invention, in the case of complete hydration, in order to obtain a polyoxyl hydrogel contact lens having an ophthalmically acceptable wettable lens surface, this is not required Entrap. Thus, in one example, the lenses of the present disclosure can comprise a wetting agent that is trapped within the lens, for example, a hydrophilic polymer and including polyvinylpyrrolidone. Alternatively, the polyoxyxahydrogel contact lenses of the present disclosure may be free of a wetting agent that is physically trapped within the lens. As used herein, physical trapping refers to the immobilization of a wetting agent or other component in the polymeric matrix of the lens with little or no chemical or chemical interaction between the wetting agent and or other components and the polymeric matrix. This is in contrast to the components that are chemically bonded to the polymeric matrix by, for example, ionic bonds, covalent bonds, van der Waals forces, and the like.

Another method commonly used in the industry to increase the wettability of polyoxyxahydrogel contact lenses involves the addition of one or more wetting agents to the polymerizable composition. In one example, the wetting agent can be a polymeric wetting agent. However, the contact lenses of the present disclosure may have an ophthalmically acceptable wettable lens surface when the polymerizable composition used to form the polymeric lens body is free of a wetting agent. Although one or more wetting agents may be included in the polymerizable compositions of the present invention to enhance the wettability of the polyoxyxahydrogel contact lenses of the present disclosure, in order to obtain an ophthalmically acceptable wettable lens surface Polyoxygenated hydrogel contact lenses, It is not necessary to include such wetting agents. In other words, in one example, the polyoxyxahydrogel contact lenses of the present disclosure can be formed from a polymerizable composition that does not contain a wetting agent. Alternatively, in another example, the polymerizable composition of the present invention may further comprise a wetting agent.

In one example, the wetting agent can be an internal wetting agent. An internal wetting agent can be incorporated into at least a portion of the lens polymeric matrix. For example, the internal wetting agent can be incorporated into at least a portion of the lens polymeric matrix by chemical bonding or another form of chemical interaction. In some cases, a wetting agent can also be bonded to the lens surface. The internal wetting agent can comprise a polymeric material or a non-polymeric material. Although one or more internal wetting agents can be incorporated into the polymeric matrix of the lenses of the present invention, in the case of complete hydration, in order to obtain a polyoxyl hydrogel contact lens having an ophthalmically acceptable wettable lens surface, and This combination is not required. Thus, in one example, a lens of the present disclosure can comprise an internal wetting agent that is bonded to at least a portion of a lens polymeric matrix. Alternatively, in another example, the polyoxyxahydrogel contact lenses of the present disclosure may be free of internal wetting agents that are incorporated into at least a portion of the lens polymeric matrix.

In another example, the wetting agent can be an internal polymeric wetting agent. The internal polymeric wetting agent can be present in the polymeric lens body as part of an interpenetrating polymer network (IPN) or a semi-IPN. The interpenetrating polymer network is formed from at least two polymers, each of which crosslinks with itself, but does not crosslink each other. Similarly, a semi-IPN is formed from at least two polymers, at least one of which is cross-linked to itself but not cross-linked to another polymer, and the other is neither cross-linked nor cross-linked to itself. In one example of the present disclosure, the polymeric lens body does not contain an internal polymeric wetting agent in the lens body in the form of IPN or semi-IPN. The contact lens can have an ophthalmically acceptable wettable lens surface. Alternatively, the contact lens can comprise an internal polymeric wetting agent in the form of an IPN or semi-IPN in the lens body.

In one example, the lens can comprise a polymeric lens body that is a reaction product of a miscible polymerizable composition, the miscible polymerizable composition comprising (a) a first oxane single represented by formula (1) body: Wherein m in the formula (1) represents an integer of 3 to 10, and n in the formula (1) represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each R ² in the formula (1) is independently a hydrogen atom or a methyl group, and the first siloxane monomer has a number average molecular weight of from 400 to 700 Daltons; (b) a second oxime An alkane monomer having a number average molecular weight greater than 7,000 Daltons, wherein the total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts to 50 unit parts; and (c) at least one a hydrophilic guanamine monomer having an N-vinyl group, the hydrophilic guanamine single system being present in the polymerizable composition in an amount of from 30 to 60 unit parts; wherein the polymerizable composition contains no polymeric internal wetting agent, The polymeric lens body is not plasma treated, and the contact lens has an ophthalmically acceptable wettable lens surface, a lens surface of a polymeric lens having a bubble trapping dynamic advancing contact angle of less than 70 degrees when fully hydrated. Optionally, the polymerizable composition may be substantially free of organic diluent, or may be substantially free of N,N-dimethyl acrylamide (DMA), may comprise at least one vinyl-containing crosslinker, or first The oxoxane monomer and the second oxoxane monomer can be present in the polymerizable composition in a ratio of from about 2:1 to about 10:1 (based on unit parts by weight), or any combination thereof.

In yet another example, the wetting agent can be attached to the link compound used to form the polymerizable composition of the lens body, or the linker physically trapped within the polymeric lens body after the lens body has been formed. When the wetting agent is a chain compound, after the lens body is polymerized or the chaining agent is trapped in the polymeric lens body, the linking compound can then link the wetting agent when the lens body is in contact with the second wetting agent. To the lens body. The link can be performed as part of the process (for example as a washing process) or can be carried out when the lens body is in contact with the packaging solution. The link may be in the form of an ionic bond or a covalent bond, or in the form of a van der Waals attraction. Chaining agent can contain Acid moiety or group, thereby allowing polymerization The acid moiety or group is present in the polymeric lens body or The acid moiety or group is physically trapped in the polymeric lens body. For example, the linker contains In the acid form, the second wetting agent may comprise a bond to A form of poly(vinyl alcohol) in acid form. Optionally, the polyoxyxahydrogel contact lenses of the present disclosure are understood to be free of chaining agents. In one example, the polyoxyl hydrogel contact lens may contain no Acid moiety or group (including polymerization Acidic moiety or group), that is, specifically, polyoxyl hydrogel contact lenses may be self-contained Acid form (for example, Acidizable form of acid, including vinyl phenyl Acid (VPB)) polymerizable composition formed, which may be derived from no Polymerizable form of acid (eg vinyl phenyl) The polymer of the unit of acid (VPB) is formed, and the polymeric lens body and the polyoxyhydrogel contact lens may not be physically trapped therein. Acid form (including Polymeric or non-polymeric form of the acid). Alternatively, the polymerizable composition, or polymeric lens body, or polyoxyhydrogel contact lens, or any combination thereof, can comprise at least one chaining agent.

In addition to including a wetting agent and modifying the surface of the lens in the polymerizable composition, the polymeric lens body has also been washed in an aqueous solution of a volatile organic solvent or a volatile organic solvent to enhance the surface of the lens. Although the polymeric lens body of the present invention can be washed in an aqueous solution of a volatile organic solvent or a volatile organic solvent in accordance with the present disclosure, in the case of complete hydration, a polyfluorene having an ophthalmically acceptable wettable lens surface is obtained. Hydrogel contact lenses do not require this wash. In other words, in one example, the polyoxyxahydrogel contact lenses of the present invention are not exposed to volatile organic solvents (including solutions of volatile organic solvents) as part of the process. In one example, the polyoxyxahydrogel contact lenses of the present invention can be formed from a polymerizable composition that does not contain a wetting agent, or the polymeric lens body and/or hydrated contact lens can be free of wetting agents or surface treated. , or without surface modification, or not exposed to volatile organic solvents during the process, or any combination thereof. Conversely, for example, the polyoxyhydrogel can be invisible in a wash solution that does not contain a volatile organic solvent (eg, water or an aqueous solution that does not contain a volatile organic solvent, including liquids that do not contain volatile lower alcohols). glasses.

The extraction of the lens body using a volatile organic solvent significantly increases the production cost due to factors such as the cost of the organic solvent, the cost of disposing of the solvent, the need to use an explosion-proof production facility, the need to remove the solvent from the lens prior to packaging, and the like. However, it has been challenging to develop polymerizable compositions that consistently produce contact lenses with ophthalmically acceptable wettable lens surfaces when extracted in aqueous liquids that do not contain volatile organic solvents. For example, it is often found in aqueous liquids that are free of volatile organic solvents. An unwet area was found on the surface of the lens from which the contact lens was taken.

As previously discussed, in one example of the present disclosure, a contact lens is a contact lens that is not exposed to a volatile organic solvent (eg, a lower alcohol) during manufacture. In other words, all liquids used in the washing, extraction, and hydrating liquids of such lenses, as well as in wet demolding, or wet delensing, or washing, or any other manufacturing step, are free of volatile organic solvents. In one example, the polymerizable composition used to form the lenses that are not in contact with the volatile organic solvent can comprise a non-vinylamine hydrophilic monomer or monomer component, for example, a hydrophilic vinyl ether containing monomer. The vinyl ether-containing monomer can include, for example, BVE, or EGVE, or DEGVE, or any combination thereof. In a particular example, the vinyl ether-containing monomer can be a vinyl ether-containing monomer that is more hydrophilic than BVE, such as DEGVE. In another example, the hydrophilic monomer component of the polymerizable composition can be a mixture of a first non-vinylamine hydrophilic monomer and a second non-vinylamine hydrophilic monomer, which is a vinyl ether monomer. . Examples of vinyl ether-containing hydrophilic monomers include, for example, BVE, or DEGVE, or EGVE, or any combination thereof.

When present, the hydrophilic vinyl ether-containing monomer or monomer component can be present in the polymerizable composition in an amount from about 1 to about 15 unit parts, or from about 3 to about 10 unit parts. When present in a mixture with a hydrophilic vinyl-containing monomer other than a vinyl ether non-vinylamine, it is not a hydrophilic vinyl-containing monomer or monomer component of a vinyl ether and a hydrophilic vinyl ether-containing monomer or single The portion of the bulk component may be based on a ratio of the unit weight parts of the hydrophilic vinyl-containing monomer or monomer component that is not a vinyl ether to the unit weight parts of the hydrophilic vinyl-containing ether monomer or monomer component, at least 3:1, or a ratio of about 3:1 to about 15:1 or about 4:1 In the polymerizable composition.

Another contact lens having an ophthalmically acceptable wettable lens surface of the present disclosure, especially a lens extracted in a liquid free of volatile organic solvents, and including lenses that are not in contact with volatile organic solvents during manufacture The method can limit the amount of the vinyl-containing crosslinker or crosslinker component included in the polymerizable composition. For example, the vinyl-containing crosslinker or crosslinker component can be from about 0.01 to about 0.80 unit parts, or from 0.01 to about 0.30 unit parts, or from about 0.05 to about 0.20 unit parts, or An amount of 0.1 unit parts is present in the polymerizable composition. In one example, the vinyl-containing crosslinker or crosslinker component can be effective to produce greater than about 2.0 unit parts, or greater than 1.0 unit parts, of the same but vinyl-containing crosslinker or crosslinker component. Number, or greater than about 0.8 unit parts, or greater than about 0.5 unit parts, or greater than about 0.3 unit parts of the contact lens resulting from a contact lens having an improved wettability compared to the amount of contact lens present in the polymerizable In the composition.

Although limiting the amount of the vinyl-containing crosslinker or crosslinker component can improve wettability, in one embodiment, including a vinyl-containing crosslinker or crosslinker component in the polymerizable composition can be improved The dimensional stability of the resulting contact lenses formed from the polymerizable composition. Thus, in some polymerizable compositions, the vinyl-containing crosslinker or crosslinker component can be effectively produced from a polymerizable composition that is the same but does not contain a vinyl-containing crosslinker or crosslinker component. Contact lenses are present in the polymerizable composition in an amount comparable to contact lenses having improved dimensional stability.

Another contact lens having an ophthalmically acceptable wettable surface of the present disclosure, especially in a liquid free of volatile organic solvents The method of the lens may be carried out in the polymerizable composition based on the unit part by weight of the hydrophilic vinylamine monomer or monomer component present in the composition and the vinyl-containing crosslinking agent present in the composition or The ratio of parts by weight of the component of the combination includes a certain amount of the vinyl-containing crosslinking agent or crosslinking agent component. For example, the total unit parts of the hydrophilic vinylguanamine monomer or monomer component and the total unit parts of the vinyl-containing crosslinker or crosslinker component can be based on all of the polymerizable composition. The ratio of the unit weight parts of the hydrophilic vinylguanamine monomer to the total unit weight parts of all vinyl-containing crosslinkers present in the polymerizable composition is greater than about 125:1, or about 150:1 to about A ratio of 625:1, or from about 200:1 to about 600:1, or from about 250:1 to about 500:1, or from about 450:1 to about 500:1, is present in the polymerizable composition.

As previously discussed, the polymerizable composition may also comprise at least one crosslinking agent, as appropriate. The optional at least one crosslinking agent can be a single crosslinking agent or can be two or more crosslinking agents in the form of a crosslinking agent component. As used herein, one or more cross-linking agent components are non-ruthenium chemistries and are therefore different from the oxoxane monomers present in the polymerizable composition, including polyfunctional oxirane monomers.

According to the present disclosure, a crosslinking agent is understood to mean a monomer having more than one polymerizable functional group (for example two or three or four polymerizable functional groups) as part of its molecular structure, ie a polyfunctional monomer, for example a double Functional or trifunctional or tetrafunctional monomer. The antimony-free crosslinking agents useful in the polymerizable compositions disclosed herein include, for example, but are not limited to, allyl (meth)acrylate, or low carbon alkylene glycol di(meth)acrylate, Or poly(lower alkylene) glycol di(meth)acrylate, or di(meth)acrylic acid low carbon alkylene Ester, or divinyl ether, or divinyl fluorene, or divinyl benzene and trivinyl benzene, or trimethylolpropane tri (meth) acrylate, or neopentyl alcohol tetra (meth) acrylate Or bisphenol A di(meth) acrylate, or methylene bis(meth) acrylamide, or triallyl phthalate and diallyl phthalate, or any A combination. Crosslinking agents as disclosed in Examples 1-25 include, for example, ethylene glycol dimethacrylate (EGDMA), or triethylene glycol dimethacrylate (TEGDMA), or triethylene glycol divinyl Ether (TEGDVE), or any combination thereof. In one example, the crosslinker can have a molecular weight of less than 1500 Daltons, or less than 1000 Daltons, or less than 500 Daltons, or less than 200 Daltons.

In one example, the crosslinker or crosslinker component can comprise or consist of a vinyl-containing crosslinker. The vinyl-containing crosslinker as used herein has at least two monomers having a polymerizable carbon-carbon double bond (ie, at least two vinyl polymerizable functional groups) present in its molecular structure, wherein the at least two Each of the polymerizable carbon-carbon double bonds in the vinyl polymerizable functional group containing a vinyl crosslinker is less reactive than the carbon present in the acrylate or methacrylate polymerizable functional group - Carbon double bond. Although as understood herein, a carbon-carbon double bond is present in the acrylate and methacrylate polymerizable functional groups, but a crosslinking agent comprising one or more acrylate or methacrylate polymerizable groups (eg, Acrylate-containing crosslinkers or methacrylate-containing crosslinkers are not considered to be vinyl-containing crosslinkers. Polymerizable functional groups having a carbon-carbon double bond which is less reactive than a carbon-carbon double bond of an acrylate or methacrylate polymerizable group include, for example, vinyl decylamine, vinyl ester, vinyl ether, and The allyl ester polymerizable functional group. Therefore, the vinyl-containing crosslinking agent used herein includes (for example) For example, a crosslinking agent having at least two polymerizable functional groups selected from the group consisting of vinyl decylamine, vinyl ether, vinyl ester, allyl ester, and any combination thereof. The mixed vinyl-containing crosslinker as used herein is a crosslinker having at least one carbon-carbon double bond present in its structure and less reactive than the acrylate or methacrylate polymerizable functional group. a polymerizable carbon-carbon double bond (ie, at least one vinyl polymerizable functional group), and at least one carbon-carbon in the structure and reactive with at least an acrylate or methacrylate polymerizable functional group A polymerizable functional group of a carbon-carbon double bond having a double bond.

In one example, the crosslinker or crosslinker component can comprise or consist of a vinyl-free crosslinker (ie, a crosslinker that is not a vinyl crosslinker). For example, the vinyl-free crosslinker or crosslinker component can comprise an acrylate-containing crosslinker (ie, a crosslinker having at least two acrylate polymerizable functional groups), or a methacrylate-containing crosslinker. A binder (ie, at least two methacrylate polymerizable functional groups), or at least one acrylate-containing crosslinking agent and at least one methacrylate-containing crosslinking agent or consist of.

The crosslinker component can comprise or consist of a combination of two or more crosslinkers each having a different polymerizable functional group. For example, the crosslinker component can comprise a vinyl-containing crosslinker and an acrylate-containing crosslinker. The crosslinker component can comprise a vinyl-containing crosslinker and a methacrylate-containing crosslinker. The crosslinker component can comprise or consist of a vinyl ether-containing crosslinker and a methacrylate-containing crosslinker.

In one example, the lens can comprise a polymeric lens body that is a reaction product of a miscible polymerizable composition, the miscible polymerizable composition comprising (a) a first oxane single represented by formula (1) body: Wherein m in the formula (1) represents an integer of 3 to 10, and n in the formula (1) represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each R ² in the formula (1) is independently a hydrogen atom or a methyl group, and the first siloxane monomer has a number average molecular weight of from 400 to 700 Daltons; (b) a second oxime An alkane monomer having a number average molecular weight greater than 7,000 Daltons, wherein the total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts to 50 unit parts; and (c) at least one a hydrophilic guanamine monomer having an N-vinyl group, the hydrophilic guanamine single system being present in the polymerizable composition in an amount of 30 to 60 unit parts; (d) at least one vinyl-containing crosslinking agent, and (e) at least one acrylate-containing crosslinker; wherein the contact lens has an ophthalmically acceptable wettable lens surface when fully hydrated. Optionally, the polymerizable composition may be substantially free of organic diluent, or may be substantially free of N,N-dimethyl decylamine (DMA), or a first oxane monomer and a second oxane. The monomer may be present in the polymerizable composition in a ratio of from about 2:1 to about 10:1 (based on unit parts by weight), or the lens may have a lens surface of a polymeric lens having a bubble-promoting dynamic advancing contact angle of less than 70 degrees, or Any combination of them.

Optionally, the polymerizable composition of the present disclosure may comprise or consist of at least one vinyl-containing crosslinker or crosslinker component and may be free of non-ruthenium non-vinyl crosslinker. In other words, in this example, the polymerizable composition comprises at least one oxoxane monomer, at least one hydrophilic monomer, and at least one crosslink Agent, wherein the at least one crosslinking agent comprises at least one vinyl-containing crosslinking agent (ie, a single vinyl-containing crosslinking agent or a vinyl-containing crosslinking agent group comprising two or more vinyl-containing crosslinking agents) The composition is due to the absence of a non-polyoxyl crosslinker other than the vinyl-containing crosslinker in the polymerizable composition. In other words, in this example, no non-vinyl crosslinker is present in the polymerizable composition.

The optional crosslinker or crosslinker component can be from 0.01 to 10.0 unit parts (eg, 0.05 to 5.0 unit parts, or 0.1 to 2.0 unit parts, or 0.2 to 1.0 unit parts, or 0.3 to 0.8 unit parts) The amount is present in the polymerizable composition. In one example, when the crosslinking agent or crosslinking agent component comprises a vinyl-containing crosslinking agent, the vinyl-containing crosslinking agent or crosslinking agent component may be 0.01 to 0.50 unit parts (for example, 0.05 to 0.30 unit parts). a quantity or a quantity of 0.1 to 0.2 unit parts) in the polymerizable composition, when the at least one crosslinking agent is an acrylate-containing or methacrylate-containing crosslinking agent or a crosslinking agent component, containing an acrylate or a The methacrylate crosslinker or crosslinker component can be present in the polymerizable composition in an amount from 0.1 to 2.0 unit parts (e.g., from 0.3 to 1.2 unit parts or from 0.5 to 0.8 unit parts). a vinyl-containing crosslinker or crosslinker component when using a vinyl-containing crosslinker or crosslinker component in combination with an acrylate-containing or methacrylate-containing crosslinker or crosslinker component The acrylate- or methacrylate-containing crosslinker or crosslinker component can be based on the unit weight part of the vinyl-containing crosslinker or crosslinker component and the acrylate-containing or methacrylate-containing crosslinker The ratio of the parts by weight of the component or the crosslinking agent component is in the polymerizable composition in a ratio of 1:2 to 1:20, or 1:3 to 1:12, or 1:4 to 1:7.

Included in the polymerizable composition a first oxoxane monomer of formula (1) and at least one When the crosslinking agent is used, the first oxoxane monomer and the at least one crosslinking agent (ie, a single crosslinking agent or a crosslinking agent component composed of two or more crosslinking agents) may be at least 10:1 (based on the total unit weight parts of the first oxoxane monomer and the total unit weight parts of the at least one crosslinking agent (ie, the unit parts of all vinyl-containing crosslinking agents present in the polymerizable composition) And the ratio) are stored in the polymerizable composition. For example, the ratio can be at least 25: 1 or at least 50: 1 or at least 100: 1 (based on unit weight parts). In one example, the at least one crosslinking agent can comprise at least one vinyl-containing crosslinking agent and at least one methacrylate-containing crosslinking agent. In another example, the at least one crosslinking agent can consist of only one or more vinyl-containing crosslinking agents. In a particular example, the at least one crosslinking agent can comprise or consist of at least one vinyl ether-containing crosslinking agent.

The at least one crosslinking agent comprises at least one vinyl-containing crosslinking agent (ie, a single vinyl-containing crosslinking agent or a vinyl-containing crosslinking agent component composed of two or more vinyl-containing crosslinking agents) Or consisting of the first oxirane monomer and the at least one vinyl-containing crosslinker based on the total number of unit parts of the first siloxane monomer and the total number of unit parts of the at least one vinyl-containing crosslinking agent The ratio of the sum of the unit parts of all vinyl-containing crosslinkers present in the polymerizable composition is present in the polymerizable composition in a ratio of at least about 50:1. For example, the ratio can be from about 50:1 to about 500:1, or from about 100:1 to about 400:1, or from about 200:1 to about 300:1 (based on unit parts by weight).

The polymerizable composition comprises a first oxoxane monomer of formula (1) and at least one other oxoxane monomer (ie, a second oxane and optionally a third oxane monomer, a fourth oxime) When alkane monomer or the like is combined with at least one crosslinking agent, the siloxane monomer and at least one vinyl-containing monomer may be based on the polymerizable group The total number of parts per unit of the oxosiloxane monomer (ie, the unit parts of the first oxane and the second oxane monomer and, if present, the third oxane monomer) And the ratio of the total number of unit parts of the at least one vinyl-containing crosslinking agent (ie, the sum of the unit parts of all vinyl-containing crosslinking agents present in the polymerizable composition) is at least about 100:1. The ratio is present in the polymerizable composition. For example, the ratio can be from about 50:1 to about 500:1, or from about 100:1 to about 400:1, or from about 200:1 to about 300:1 (based on unit parts by weight).

Additionally, the polymerizable compositions of the present disclosure may optionally comprise at least one non-hydrazine hydrophobic monomer. A hydrophobic monomer is understood to be a non-polyoxyl polymerizable component having only one polymerizable functional group present in its molecular structure. The at least one hydrophobic monomer of the polymerizable composition may be a hydrophobic monomer or may comprise a hydrophilic monomer component composed of at least two hydrophilic monomers. Examples of hydrophobic monomers useful in the polymerizable compositions disclosed herein include, but are not limited to, acrylate containing hydrophobic monomers or methacrylate containing hydrophobic monomers or any combination thereof. Examples of hydrophobic monomers include, but are not limited to, methyl acrylate, or ethyl acrylate, or propyl acrylate, or isopropyl acrylate, or cyclohexyl acrylate, or 2-ethylhexyl acrylate, or methacrylic acid. Methyl ester (MMA), or ethyl methacrylate, or propyl methacrylate, or butyl acrylate, or vinyl acetate, or vinyl propionate, or vinyl butyrate, or vinyl valerate Ester, or styrene, or chloroprene, or vinyl chloride, or dichloroethylene, or acrylonitrile, or 1-butene, or butadiene, or methacrylonitrile, or vinyl toluene, or ethylene Ethyl ethyl ether, or perfluorohexylethyl thiocarbonylaminoethyl methacrylate, or isodecyl methacrylate, or trifluoroethyl methacrylate, or hexafluoroisopropyl methacrylate Ester, or Hexafluorobutyl methacrylate, or ethylene glycol methyl ether methacrylate (EGMA), or any combination thereof. In a particular example, the hydrophobic monomer or monomer component can comprise or consist of MMA or EGMA or both.

When present in the polymerizable composition, the hydrophobic monomer or monomer component can be present in an amount from about 5 to about 25 unit parts, or from about 10 to about 20 unit parts.

In one example, the hydrophobic monomer component can comprise at least two hydrophobic monomers each having a different polymerizable functional group. In another example, the hydrophobic monomer component can comprise at least two hydrophobic monomers each having the same polymerizable functional group. The hydrophobic monomer component can comprise or consist of two hydrophobic monomers each having the same polymerizable functional group. In one example, the hydrophobic monomer component can comprise or consist of two hydrophobic methacrylate containing monomers. The hydrophobic monomer component can comprise or consist of MMA and EGMA. In one example, at least two hydrophobic monomers of the hydrophobic monomer component may comprise or consist of MMA and EGMA, and the ratio of the unit parts of the MMA stored in the polymerizable composition to the unit parts of the EGMA may be It is about 6:1 to about 1:1. The ratio of the unit parts of MMA to EGMA in the polymerizable composition may be about 2:1 (unit parts based on MMA and unit parts of EGMA).

In one example, the lens can comprise a polymeric lens body that is a reaction product of a miscible polymerizable composition, the miscible polymerizable composition comprising (a) a first oxane single represented by formula (1) body: Wherein m in the formula (1) represents an integer of 3 to 10, and n in the formula (1) represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each R ² in the formula (1) is independently a hydrogen atom or a methyl group, and the first siloxane monomer has a number average molecular weight of from 400 to 700 Daltons; (b) a second oxime An alkane monomer having a number average molecular weight greater than 7,000 Daltons, wherein the total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts to 50 unit parts; (c) at least one of An N-vinyl hydrophilic guanamine monomer, the hydrophilic guanamine single system being present in the polymerizable composition in an amount of 30 to 60 unit parts; and (d) at least one hydrophobic monomer, wherein the contact lens An ophthalmically acceptable wettable lens surface when fully hydrated. Optionally, the polymerizable composition may be substantially free of organic diluent, or may be substantially free of N,N-dimethyl acrylamide (DMA), may comprise at least one vinyl-containing crosslinker, or first The oxoxane monomer and the second oxoxane monomer may be present in the polymerizable composition in a ratio of from about 2:1 to about 10:1 (based on unit parts by weight), or the lens may have a bubble-forming dynamic advancing contact angle The lens surface of the polymeric lens of less than 70 degrees, or any combination thereof.

The polymerizable composition may optionally include one or more organic diluents, one or more polymerization initiators (ie, ultraviolet (UV) initiators or hot initiators or both), or one or more UV absorbers, or One or more color formers, or one or more oxygen scavengers, or one or more chain transfer agents, or any combination thereof. These optional ingredients may be reactive or non-polymerizable. In one example, the polymerizable composition may be free of diluents because it does not contain any between the oxirane and other lens forming ingredients (eg, optional hydrophilic monomers, hydrophobic monomers, and crosslinkers). Miscible organic thinner. Additionally, a plurality of the polymerizable compositions of the present invention are substantially free of water (e.g., contain no more than by weight) 3.0% or 2.0% water).

The polymerizable compositions disclosed herein may optionally comprise one or more organic diluents, i.e., the polymerizable composition may comprise an organic diluent, or may comprise an organic diluent component having two or more organic diluents. Organic diluents which may optionally be included in the polymerizable compositions of the present invention include alcohols, including lower alcohols such as, but not limited to, pentanol, or hexanol, or octanol, or decyl alcohol, or any combination thereof . Where the organic diluent or organic diluent component is included, it may be from about 1 to about 70 unit parts, or from about 2 unit parts to about 50 unit parts, or from about 5 unit parts to about 30 unit parts. The amount is provided in the polymerizable composition.

The polymerizable composition of the present invention may optionally comprise one or more polymerization initiators, i.e., the polymerizable composition may comprise an initiator, or may comprise an initiator component having two or more polymerization initiators. The polymerization initiator which may be included in the polymerizable composition of the present invention includes, for example, an azo compound or an organic peroxide or both. The initiators which may be present in the polymerizable composition include, for example but are not limited to, benzoin ethyl ether, or benzyldimethylketal, or α,α-diethoxyacetophenone, or 2. 4,6-trimethylbenzimidyldiphenylphosphine oxide, or peroxidized benzoin, or tributyl peroxide, or azobisisobutyronitrile, or azobisdimethylvaleronitrile, or Any combination. The UV photoinitiator may include, for example, a phosphine oxide such as diphenyl (2,4,6-trimethylbenzimidyl)phosphine oxide, or benzoin methyl ether, or 1-hydroxycyclohexyl phenyl ketone. Or Darocur (available from BASF, Florham Park, NJ, USA), or Irgacur (also available from BASF), or any combination thereof. In many of the examples 1-25 disclosed herein, the polymerization initiator is a thermal initiator 2,2'-azobis- 2-Methylpropionitrile (VAZO-64 from E.I. DuPont de Nemours & Co., Wilmington, DE, USA). Other commonly used thermal initiators may include 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO-52) and 1,1'-azobis(cyanocyclohexane) (VAZO) -88). The polymerization initiator or initiator component may be in an amount of from about 0.01 unit parts by weight to about 2.0 unit parts by weight, or from about 0.1 unit parts by weight to about 1.0 unit parts by weight, or about 0.2 unit parts by weight. The amount is up to about 0.6 unit parts by weight in the polymerizable composition.

Optionally, the polymerizable composition of the present invention may comprise one or more UV absorbers, i.e., the polymerizable composition may comprise a UV absorber, or may comprise a UV absorber component having two or more UV absorbers. UV absorbers which may be included in the polymerizable compositions of the present invention include, for example, diphenyl ketone, or benzotriazole, or any combination thereof. In many of the examples 1-25 disclosed herein, the UV absorber is 2-(4-benzylidene-3-hydroxyphenoxy)ethyl acrylate (UV-416) or methacrylic acid 2- (3-(2H-benzotriazol-2-yl)-4-hydroxy-phenyl)ethyl ester (NORBLOC® 7966 from Noramco, Athens, GA, USA). The UV absorber or UV absorber component may be in an amount of from about 0.01 unit parts by weight to about 5.0 unit parts by weight, or from about 0.1 unit parts by weight to about 3.0 unit parts by weight, or from about 0.2 unit parts by weight to An amount of about 2.0 unit parts by weight is present in the polymerizable composition.

The polymerizable compositions of the present disclosure may also optionally include at least one color former (i.e., a color former or a colorant component comprising two or more colorants), but encompasses a pigmented and transparent lens product. In one example, the colorant can be a reactive dye or pigment that effectively provides color to the resulting lens product. The color former or colorant component of the polymerizable composition can comprise a polymerizable colorant, or can comprise a non-polymerizable colorant, or any combination thereof. The polymerizable colorant may be a coloring agent whose molecular structure contains a polymerizable functional group, or may be a coloring agent whose molecular structure includes both a monomer part and a dye part, that is, the coloring agent may be a monomer-dye compound. The molecular structure of the colorant may comprise a β碸 functional group, or may comprise three Functional group. Colorants can include, for example, VAT Blue 6 (7,16-dichloro-6,15-dihydroanthracene). -5,9,14,18-tetraketone), or 1-amino-4-[3-(β-sulfatoethylsulfonyl)anilino]-2-indolesulfonic acid (CI reactivity) Blue 19, RB-19), or monomeric-dye compound (RB-19 HEMA) of reactive blue 19 and hydroxyethyl methacrylate, or 1,4-bis[4-[(2-methylpropene) Mercapto-oxyethyl)phenylamino]phosphonium (Reactive Blue 246, RB-246, available from Arran Chemical, Athlone, Ireland), or 1,4-bis[(2-hydroxyethyl) Amino]-9,10-nonanedione bis(2-acrylic acid) ester (RB-247), or reactive blue 4 (RB-4), or a combination of reactive blue 4 and hydroxyethyl methacrylate Body-dye compound (RB-4 HEMA or "blue HEMA"), or any combination thereof. In one example, the colorant or colorant component can comprise a polymerizable colorant. The polymerizable colorant component can comprise, for example, RB-246, or RB-274, or RB-4 HEMA, or RB-19 HEMA, or any combination thereof. Examples of monomer-dye compounds include RB-4 HEMA and RB-19 HEMA. Further examples of monomer-dye compounds are described in US Pat. No. 5,944, 853 and US Pat. Other exemplary colorants are disclosed in, for example, U.S. Patent Application Publication No. 2008/0048350, the disclosure of which is incorporated herein in its entirety by reference. In many of the examples 1-25 disclosed herein, the colorants are reactive blue dyes, such as those described in US Pat. No. 4,997,897, the disclosure of which is incorporated herein in its entirety by reference. Other suitable colorants for use in accordance with the present invention are phthalocyanine pigments (e.g., phthalocyanine blue or phthalocyanine green), or chromium-aluminum-cobalt oxides, or chromium oxides and various red, yellow, brown, and black iron oxides, Or any combination thereof. An opacifier such as titanium dioxide may also be incorporated. For some applications, a combination of colorants having different colors can be employed as the colorant component. If utilized, the colorant or colorant component can range from about 0.001 unit parts to about 15.0 unit parts, or from about 0.005 unit parts to about 10.0 unit parts, or from about 0.01 unit parts to about 8.0 unit parts. The amount in the range is in the polymerizable composition.

The polymerizable composition of the present disclosure may optionally comprise at least one oxygen scavenger, i.e., an oxygen scavenger or an oxygen scavenger component comprising two or more oxygen scavengers. Examples of the oxygen scavenger which can be used as the oxygen scavenger or oxygen scavenger component of the polymerizable composition of the present invention include, for example, vitamin E, or a phenolic compound, or a phosphite compound, or a phosphine compound, or an amine oxide. a compound, or any combination thereof. For example, the oxygen scavenger or oxygen scavenger component can be comprised of or comprise the phosphine containing compound. In many of the examples 1-25 disclosed herein, the oxygen scavenger or oxygen scavenger component is a polymerizable form of a phosphine compound, such as triphenylphosphine, or triphenylphosphine (eg, diphenyl (p-vinyl) Phenyl) phosphine).

Chain transfer is a polymerization reaction that transfers the activity of a growing polymer chain to another molecule, thereby reducing the average molecular weight of the final polymer. The polymerizable composition of the present disclosure may optionally comprise at least one chain transfer agent, i.e., may comprise a chain transfer agent or may comprise a chain transfer agent component having at least two chain transfer agents. Chain transfer agent or chain which can be used as the polymerizable composition of the present invention Examples of the chain transfer agent included in the transfer component include, for example, a thiol compound, or a halogen carbon compound, or a C3-C5 hydrocarbon, or any combination thereof. In many of the examples 1-25 disclosed herein, the chain transfer agent is allyloxyethanol. When present in the polymerizable composition, the chain transfer agent or chain transfer agent component can be present in an amount from about 0.01 unit parts to about 1.5 unit parts, for example from about 0.1 unit parts to about 0.5 unit parts.

The resulting polyoxyxahydrogel contact lenses can have a high equilibrium water content (EWC) due to the large amount of one or more hydrophilic vinyl guanamine monomers present in the disclosed polymerizable composition. Methods for determining EWC are known to those skilled in the art and can be based on the weight lost from the lens during the drying process. For example, a polyoxyxahydrogel contact lens can have an equilibrium water content of from 20% to 75% by weight when fully hydrated. The contact lens of the present invention may have from about 30% to about 70% by weight, or from about 45% to about 65% by weight, or from about 50% to about 67% by weight, or from about 50% to about 63% by weight, or From about 55% by weight to about 65% by weight of EWC.

In one example, the contact lenses of the present disclosure are ophthalmically compatible polyoxyxahydrogel contact lenses. As will be discussed below, a number of different criteria can be evaluated to determine if a contact lens is ophthalmically compatible. In one example, an ophthalmically acceptable contact lens has an ophthalmically acceptable wettable surface when fully hydrated. A polyoxyl hydrogel contact lens having an ophthalmically acceptable wettable surface is understood to mean an adverse effect on the tear film of the lens wearer's eye that has not been achieved by the lens wearer to experience or report with the eye. Or a polyoxyl hydrogel contact lens to the extent of discomfort associated with polyoxyl hydrogel contact lenses.

One method of assessing the wettability of a lens surface is to measure the bubble-forming dynamic advancing contact angle of the surface. The polyoxyxahydrogel contact lens of the present invention may have a bubble-catching dynamic advancing contact angle of less than 120 degrees, for example, less than 90 degrees when fully hydrated, less than 80 degrees when fully hydrated, and less than 70 degrees when fully hydrated, or Less than 65 degrees when fully hydrated, or less than 60 degrees when fully hydrated, or less than 50 degrees when fully hydrated.

Another method of assessing the wettability of the lens surface is to measure the static trapping angle of the lens surface. The polyoxyxahydrogel contact lenses of the present invention may have less than 70 degrees when fully hydrated, or less than 60 degrees when fully hydrated, or less than 55 degrees when fully hydrated, or less than 50 degrees when fully hydrated, or may be completely The static trapping angle of the trapping bubble is less than 45 degrees when hydrated.

The contact lens of the present invention may have an oxygen permeability (or Dk) of at least 55 barrer when fully hydrated (Dk 55barrer) or at least 60barrer oxygen permeability (Dk 60barrer), or at least 65barrer oxygen permeability (Dk 65barrer). The lens may have an oxygen permeability of from about 55 barrer to about 135 barrer, or from about 60 barrer to about 120 barrer, or from about 65 barrer to about 90 barrer, or from about 50 barrer to about 75 barrer. A variety of methods for determining oxygen permeability are known to those skilled in the art.

The polyoxyxahydrogel contact lenses of the present disclosure may have an average tensile modulus of from about 0.20 MPa to about 0.90 MPa when fully hydrated. For example, the average modulus can be from about 0.30 MPa to about 0.80 MPa, or from about 0.40 MPa to about 0.75 MPa, or from about 0.50 MPa to about 0.70 MPa.

The modulus of a contact lens or lens body as used herein is understood to mean the modulus of tension, also known as the Young's modulus. Elastic material The measure of stiffness. Tensile modulus can be measured using methods that conform to the ANSI Z80.20 standard. In one example, the tensile modulus can be measured using an Instron Model 3342 or Model 3343 mechanical test system.

The contact lens of the present invention may have an oxygen permeability of at least 55 barrer when fully hydrated (Dk 55 barrer), or about 30% to about 70% EWC, or a tensile modulus of from about 0.2 MPa to about 0.9 MPa, or any combination thereof. In one example, the contact lens can have an oxygen permeability of at least 60 barrer (Dk 60 barrer), or about 35% to about 65% EWC, or a tensile modulus of from about 0.3 MPa to about 0.8 MPa, or any combination thereof. In another example, the contact lenses of the present invention may have an oxygen permeability of at least 60 barrer, or an EWC of from about 45% to about 65%, or a tensile modulus of from about 0.40 MPa to about 0.75 MPa, or any of them, when fully hydrated. A combination.

In one example, the contact lenses of the present invention can have an oxygen permeability of at least 55 barrer, or an EWC of from about 30% to about 70%, or a tensile modulus of from about 0.2 MPa to about 0.9 MPa, or any of them, when fully hydrated. combination.

The polyoxyxahydrogel contact lenses of the present disclosure may have an average energy loss percentage of from about 25% to about 40% when fully hydrated. For example, the average energy loss percentage can be from about 27% to about 40%, or can be from about 30% to about 37%.

The percent energy loss used herein is a measure of the amount of energy lost as heat in the application of a loading and energy release cycle to a viscoelastic material. The percentage of energy loss can be determined using a variety of methods known to those skilled in the art. For example, the force involved in stretching the sample to 100% strain at a constant rate and then recovering it to 0% can be determined and used to calculate the energy loss of the material. Lost percentage.

The contact lens of the present invention may have an ion current of less than about 8.0 x 10 ^-3 mm ² /min, or less than about 7.0 x 10 ^-3 mm ² /min, or less than about 5.0 x 10 ^-3 mm ² /min when fully hydrated. . Various methods of determining ion current are conventional methods and are known to those skilled in the art.

In one example, the contact lenses of the present invention can have a wet extractable component. The wet extractable components are determined based on the weight loss of the contact lenses during methanol extraction, which are fully hydrated and sterilized prior to drying and extraction testing. The wet extractable component can comprise an unreacted or partially reacted polymerizable component of the polymerizable composition. For lenses formed from a polymerizable composition comprising a non-polymerizable component, the wet extractable component is comprised of an organic solvent extractable material that remains in the lens body after the lens body has been fully processed to form a sterile contact lens. For lenses extracted in extracts containing volatile organic solvents or extracts containing no organic solvents during manufacture, in most cases, substantially all non-polymerizable components have been removed from the lens body and are wet extractable The component may thus consist essentially of an extractable component formed from the reactive polymerizable component of the polymerizable composition (i.e., the unreacted polymerizable component and the partially reacted polymerizable component). In lenses prepared from a diluent-free polymerizable composition, the wet extractable component can be from about 1% wt/wt to about 15% wt/wt, or about 2%, based on the dry weight of the lens body prior to the extraction test. An amount of wt/wt to about 10% wt/wt, or about 3% wt/wt to about 8% wt/wt is present in the contact lens. In a lens prepared from a polymerizable composition comprising a diluent, the wet extractable component can be comprised of a portion of the diluent and the unreacted and partially reacted polymerizable component, and can be based on the lens body prior to the extraction test The dry weight is from about 1% wt/wt to about 20% wt/wt, or from about 2% wt/wt to about 15% wt/wt, or from about 3% wt/wt to about 10% wt/wt. The amount is stored in the contact lens.

In one example, the contact lenses of the present invention have a dry extractable component. The dry extractable fraction is determined based on the weight loss of the polymeric lens body during methanol extraction, which has not been washed, extracted (as part of the process), hydrated or sterilized prior to drying and extraction testing. The dry extractable component can comprise an unreacted or partially reacted polymerizable component of the polymerizable composition. The dry extractable component may further comprise a non-polymerizable component when an optional non-polymerizable component such as a diluent and the like is present in the polymerizable composition.

In lenses prepared from a polymerizable composition that does not contain a diluent, the dry extractable component of the lens is primarily contributed by the polymerizable component of the polymerizable composition (i.e., unreacted or partially reacted polymerizable component). The dry extractable component composition may also include a small amount (eg, less than 3% wt/wt) of optional non-polymerizable components (eg, colorants, oxygen scavengers, and the like) present in the polymerizable composition. Dry extractable material. In a lens prepared from a diluent-free polymerizable composition, the dry extractable component can be based on the dry weight of the lens body prior to the extraction test to be from about 1% wt/wt to about 30% wt/wt of the lens body, or From about 2% wt/wt to about 25% wt/wt, or from about 3% wt/wt to about 20% wt/wt, or from about 4% wt/wt to about 15% wt/wt, or 2% wt/wt It is present in the polymeric lens body in an amount of less than 10% wt/wt.

In a lens prepared from a polymerizable composition comprising a large amount (eg, greater than 3% wt/wt) of an optional non-polymerizable component such as a diluent, the dry extractable group The fraction consists of an extractable material contributed by the reactive component and an extractable component contributed by the non-polymerizable component of the polymerizable composition. The total amount of dry extractable components contributed by the reactive component and the non-polymerizable component present in the contact lens may be from about 1% wt/wt to about 75% wt% of the lens based on the dry weight of the polymeric lens body prior to the extraction test. Wt, or from about 2% wt/wt to about 50% wt/wt, or from about 3% wt/wt to about 40% wt/wt, or from about 4% wt/wt to about 20% wt/wt, or about 5 From about 10% to about 10%. The total amount of dry extractable components contributed by the polymerizable component (ie, unreacted or partially reacted polymerizable component) may be from about 1% wt/wt to about 30% of the lens body based on the dry weight of the lens body prior to the extraction test. Wt/wt, or from about 2% wt/wt to about 25% wt/wt, or from about 3% wt/wt to about 20% wt/wt, or from about 4% wt/wt to about 15% wt/wt, or An amount from 2% wt/wt to less than 10% wt/wt.

Some specific examples of polyoxyxahydrogel contact lenses will now be set forth in accordance with the teachings of the present invention.

As an example (Example A), a polyoxyxahydrogel contact lens comprises a polymeric lens body which is a reaction product of a polymerizable composition comprising: a first oxirane represented by formula (1) a monomer, wherein m in the formula (1) represents an integer of 3 to 10, and n in the formula (1) represents an integer of 1 to 10, and the R ¹ in the formula (1) has 1 to 4 carbon atoms An alkyl group, and each of R ² in formula (1) is independently a hydrogen atom or a methyl group, and the first oxane has a number average molecular weight of from 400 to 700 Daltons; the second oxane is a single a body having a number average molecular weight greater than 7,000 Daltons; wherein the total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts by weight to 50 unit parts by weight; and having one N-ethylene a hydrophilic guanamine monomer or monomer component, wherein the hydrophilic monomer or monomer component is present in the polymerizable composition in an amount of from 30 to 60 parts, and the polymeric lens body is ophthalmically acceptable Wettable surface. In particular, the hydrophilic vinyl guanamine monomer may comprise or consist of N-vinyl-N-methylacetamidine (VMA).

As a second example (Example B), the polyoxyxahydrogel contact lens comprises a polymeric lens body which is the reaction product of the polymerizable composition of Example A, and wherein the polymerizable composition further comprises a non-vinyl fluorene An amine hydrophilic monomer or monomer component comprising or consisting of a vinyl ether containing monomer or monomer component.

As a third example (Example C), the polyoxyxahydrogel contact lens comprises a polymeric lens body which is the reaction product of the polymerizable composition as described in Example A or B, and wherein the polymerizable composition further comprises a hydrophobic The monomer or monomer component, in particular, the hydrophilic monomer comprises or consists of methyl methacrylate (MMA).

As a fourth example (Example D), the polyoxyxahydrogel contact lens comprises a polymeric lens body which is the reaction product of a polymerizable composition as described in Example A or B or C, and wherein the polymerizable composition is further A vinyl-containing crosslinker or crosslinker component is included. In one example, the crosslinker or crosslinker component can comprise or consist of a vinyl ether containing crosslinker or crosslinker component, in particular the crosslinker or crosslinker component can comprise triethyl Diol divinyl ether (TEGVE) or consists of it.

As a fifth example (Example E), the polyoxyxahydrogel contact lens comprises a polymeric lens body which is the reaction product of a polymerizable composition as described in Example A or B or C or D, and wherein the polymerizable combination Further includes a hot start Agent or hot starter component.

As a sixth example (Example F), the polyoxyxahydrogel contact lens comprises a polymeric lens body which is the reaction product of the polymerizable composition as described in Example A or B or C or D or E, and wherein The polymeric composition further comprises an oxygen scavenger or oxygen scavenger component.

As a seventh example (Example G), the polyoxyxahydrogel contact lens comprises a polymeric lens body which is the reaction product of the polymerizable composition as described in Example A or B or C or D or E or F, and wherein The polymerizable composition further comprises a UV absorber or UV absorber component.

As an eighth example (Example H), the polyoxyxahydrogel contact lens comprises a polymeric lens body which is the reaction product of the polymerizable composition as described in Example A or B or C or D or E or F or G, And wherein the polymerizable composition further comprises a colorant or a colorant component.

As a ninth example (Example I), a polyoxyxahydrogel contact lens comprises a polymeric lens body which is reacted as described in Example A or B or C or D or E or F or G or H in a polymerizable composition a product, and wherein the polymerizable composition further comprises a second oxoxane monomer represented by the above formula (2), wherein R ₁ in the formula (2) is selected from a hydrogen atom or a methyl group; R _{2 is} selected from hydrogen or a hydrocarbon group having 1 to 4 carbon atoms; m in the formula (2) represents an integer of 0 to 10; n in the formula (2) represents an integer of 4 to 100; a and b represent 1 or A larger integer; a+b is equal to 20-500; b/(a+b) is equal to 0.01-0.22; and the configuration of the oxoxane unit includes a random configuration. As an example, the second oxane monomer can be represented by the above formula (2), wherein m in the formula (2) is 0, and n in the formula (2) is an integer of 5 to 10, and a is a 65 to An integer of 90, b is an integer of 1 to 10, R ₁ in the formula (2) is a methyl group, and R ₂ in the formula (2) is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

As a tenth example (Example J), the polyoxyxahydrogel contact lens comprises a polymeric lens body, such as the polymerizable composition of Example A or B or C or D or E or F or G or H or I. a reaction product, and wherein the polymerizable composition further comprises a methacrylate-containing crosslinking agent or a crosslinking agent component, in particular, the crosslinking agent or crosslinking agent component may comprise ethylene glycol dimethacrylate (EGDMA) or consists of it. In this example, where the polymerizable composition also comprises a vinyl ether-containing crosslinker as part of the crosslinker component, in particular the crosslinker component may comprise triethylene glycol divinyl ether (TGDVE) In combination with or consisting of a methacrylate containing crosslinker, it may in particular comprise or consist of ethylene glycol dimethacrylate (EGDMA). In this example, it is understood that the polymerizable composition comprises two crosslinkers, each having a different reactivity ratio, ie, the polymerizable composition contains a vinyl-containing crosslinker and a methacrylate-containing crosslinker. Or a crosslinker component consisting of the same, the methacrylate-containing crosslinker having a higher reactivity than the vinyl polymerizable functional group present in the vinyl-containing crosslinker and thus at a faster rate The polymerizable functional group of the reaction.

As an eleventh example (Example K), the polyoxyxahydrogel contact lens comprises a polymeric lens body as described in Example A or B or C or D or E or F or G or H or I or J. The reaction product of the polymeric composition, and wherein the polymerizable composition further comprises a chain transfer agent or a chain transfer agent component, which may specifically comprise or consist of allyloxyethanol (AE).

As a twelfth example (Example L), a polyoxyl hydrogel contact lens comprises a polymeric lens body which is a reaction product of a polymerizable composition as described in Example A or B or C or D or E or F or G or H or I or J or K, and wherein the polymerizable composition further comprises a non- A vinylguanamine hydrophobic monomer or hydrophobic monomer component, which may specifically comprise or consist of ethylene glycol methyl ether methacrylate (EGMA).

As a thirteenth example (Example M), a polyoxyxahydrogel contact lens comprises a polymeric lens body such as Example A or B or C or D or E or F or G or H or I or J or K or L The reaction product of the polymerizable composition, and wherein the polymerizable composition further comprises a non-vinylamine hydrophilic vinyl-containing ether monomer or monomer component, for example, a hydrophilic vinyl ether-containing monomer or monomer The component may comprise or consist of 1,4-butanediol vinyl ether (BVE), or ethylene glycol vinyl ether (EGVE), or diethylene glycol vinyl ether (DEGVE), or any combination thereof .

As a fourteenth example (Example N), the polyoxyxahydrogel contact lens comprises a polymeric lens body such as Example A or B or C or D or E or F or G or H or I or J or K or L Or the reaction product of the polymerizable composition of M, wherein the polymerizable composition used to form the lens does not contain an internal wetting agent, or the polymerizable composition used to form the polymeric lens body does not contain an organic diluent When the extraction lens main system is extracted in a liquid containing no volatile organic solvent, or when the lens is not subjected to surface plasma treatment, or any combination thereof, the contact lens has an ophthalmically acceptable wettable lens surface.

In any or each of the above examples AN, and any or all of the other examples disclosed herein, the amount of the first oxoxane monomer can range from 20 to 45 unit parts of the polymerizable composition. . The amount of the first oxane monomer can account for 25 to 40 unit parts of the polymerizable composition. The amount of the first oxoxane monomer may range from 27 to 35 unit parts of the polymerizable composition.

In any or each of the above examples AN, and any or all of the other examples disclosed herein, the amount of the second oxoxane monomer may range from 1 to 20 unit parts of the polymerizable composition. . The amount of the second oxane monomer may range from 2 to 15 unit parts of the polymerizable composition. The amount of the second oxane monomer may range from 5 to 13 unit parts of the polymerizable composition. In another example, the ratio of the unit parts of the first oxoxane monomer to the second oxane may be at least 1:1, or at least 2:1.

In any or each of the above examples AN, and any or all of the other examples disclosed herein, the amount of hydrophilic monomer or monomer component present in the polymerizable composition may comprise polymerizable 1 to 60 unit parts of the composition. The hydrophilic monomer component can constitute from 4 to 60 unit parts of the polymerizable composition. When the hydrophilic monomer comprises or consists of VMA, it may be present in an amount of from 30 to 60 unit parts. VMA can be present in the polymerizable composition in an amount from about 40 unit parts to about 50 unit parts. In hydrophilic monomer (ie N,N-dimethyl acrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA) or 2-hydroxybutyl methacrylate (HOB), or any Combinations) When the hydrophilic monomer in the hydrophilic monomer component is present in the polymerizable composition, each or all may be present in an amount of from about 3 to about 10 unit parts.

In any or each of the above examples AN and any or all of the other examples disclosed herein, the amount of hydrophobic monomer or monomer component present in the polymerizable composition may comprise a polymerizable composition 1 to 30 unit parts. For example, the total amount of hydrophobic monomer or monomer component may constitute the polymerizable composition. From about 5 to about 20 unit parts. In the polymerizable composition in which the hydrophobic monomer MMA is present as a hydrophobic monomer or as part of a hydrophobic monomer component, the MMA may be present in an amount of from about 5 to about 20 unit parts, or from about 8 to about 15 unit parts. .

In any or each of the above examples AN, and any or all of the other examples disclosed herein, the amount of crosslinker or crosslinker component present in the polymerizable composition may comprise 0.01 to 4 unit parts of the polymeric composition. TEGDVE can be present in an amount from 0.01 to 1.0 unit parts. EGDMA may be present in an amount from 0.01 to 1.0 unit parts. TEGDMA can be present in an amount from 0.1 to 2.0 unit parts. Each of the non-ruthenium crosslinkers may be present in the polymerizable composition either alone or in any combination.

In any or each of the above examples AN and any or all of the other examples disclosed herein, when the polymerizable composition comprises EGMA, BVE, DEGVE, EGVE, or any combination thereof, each of its It is present in an amount from 1 unit part to 20 unit parts of the polymerizable composition. EGMA can be present in an amount from about 2 unit parts to about 15 unit parts. BVE can be present in an amount from 1 unit part to about 15 unit parts. BVE can be present in an amount from about 3 unit parts to about 7 unit parts. DEGVE can be present in an amount from 1 unit part to about 15 unit parts. DEGVE can be present in an amount from about 7 unit parts to about 10 unit parts. EGVE can be present in an amount from 1 unit part to about 15 unit parts, or from about 3 unit parts to about 7 unit parts.

In any or each of the above examples AN, and any or all of the other examples disclosed herein, other optional components (eg, starter or starter components, colorants, or colorants) Component, UV absorber or UV absorption The receiving component, the oxygen scavenger or oxygen scavenger component, or the chain transfer agent or chain transfer agent component can each be present in an amount from about 0.01 unit parts to about 3 unit parts. The starter or starter component can be present in the polymerizable composition in an amount from 0.1 unit parts to 1.0 unit parts. It may be present in an amount from about 0.3 to about 0.5 unit parts in the presence of a hot starter or hot starter component (e.g., Vazo-64). The colorant or colorant component may be present in an amount from 0.01 unit parts to 1 unit part. When a reactive dye (e.g., reactive blue 246 or reactive blue 247) is used as a colorant or as part of a colorant component, it can each be present in an amount of about 0.01 unit parts. The UV absorber or UV absorber component may be present in an amount from 0.1 unit parts to 2.0 unit parts. For example, the UV absorber UV1 described in Examples 1-25 below may be present in an amount from about 0.8 to about 1.0 unit parts (eg, 0.9 unit parts); or the UV absorbers described in Examples 1-25 below. UV2 can be present in an amount from 0.5 unit parts to 2.5 unit parts (eg, from about 0.9 unit parts to about 2.1 unit parts). The oxygen scavenger or oxygen scavenger component may be present in an amount from 0.1 unit parts to 1.0 unit parts. As an example, when triphenylphosphine (TPP) or diphenyl (p-vinylphenyl) phosphine (pTPP) or any combination thereof is used as the oxygen scavenger or oxygen scavenger component in the polymerizable composition, Each or combination may be present in an amount from 0.3 unit parts to 0.7 unit parts (eg, about 0.5 unit parts). The chain transfer agent or chain transfer agent component may be present in the polymerizable composition in an amount from 0.1 unit parts to 2.0 unit parts, and in parts of Examples 1-25 below, from 0.2 unit parts to 1.6 unit parts. The amount exists. For example, the chain transfer agent allyloxyethanol (AE) can be present in an amount from about 0.3 to about 1.4 unit parts.

In any or each of the above examples AN, and any or all of the other examples disclosed herein, the polyoxyxahydrogel contact lens may be absent from the polymerizable composition or may be present in the polymerization. A wetting agent in the lens body or in a polyoxygen hydrogel contact lens. Similarly, polyoxyxahydrogel contact lenses can have lens surfaces that have not been surface treated or surface modified. However, in another example, the polyoxyxahydrogel contact lens can include at least one wetting agent in the polymerizable composition, in the polymeric lens body, or in the polyoxyxahydrogel contact lens (ie, A single wetting agent or two or more wetting agents present as a wetting agent component). Polyoxygenated hydrogel contact lenses can have treated or modified lens surfaces. Additionally or alternatively, any or all of the foregoing example AN, and any or all other examples of the polyoxyxahydrogel contact lenses disclosed herein, the contact lens can be understood to be free of a linker (eg, Acid form).

In another example, a new polymerizable composition is provided, including each of the polymerizable compositions set forth herein with reference to a polyoxyl hydrogel contact lens and method. The polymerizable composition may be free of diluents because it does not contain organic solvents (e.g., alcohols and the like) which may help reduce phase separation of the polymerizable composition. However, the diluent-free polymerizable compositions may still contain one or more chain transfer agents, such as allyloxyethanol. However, if desired, the polymerizable composition can include a diluent or diluent component which can be present in an amount from 1 to 20 unit parts.

As described herein, a polyoxyxahydrogel contact lens of the present invention comprising a polymeric lens body has an ophthalmically acceptable wettable surface comprising a first oxoxane derived from the formula (1). Monomeric, optional second oxane monomer (eg, having more than one functional group and number average molecular weight a second oxoxane monomer in an amount of at least 3,000 Daltons, such as those represented by formula (2), (3) or (4), the first hydrophilic monomer or monomer component being An amount of 30 to 60 unit parts is present in the polymerizable composition. In one example, the polyoxyl hydrogel contact lens can also be dimensionally stable. Accordingly, the present disclosure is also directed to a batch of polyoxygen hydrogel contact lenses.

As used herein, a batch of polyoxyhydrogel contact lenses refers to a group of two or more polyoxyhydrogel contact lenses, and typically, a batch refers to at least 10, or at least 100 , or at least 1,000 polyoxyhydrogel contact lenses. In accordance with the present disclosure, a batch of polyoxyxahydrogel contact lenses comprise any of a plurality of polyoxyhydrogel contact lenses described herein.

In one example, the batch of polyoxyhydrogel contact lenses comprises a plurality of contact lenses of the present disclosure, wherein the batch is based on an average of values measured for at least 20 individual lenses in the batch Polyoxyl hydrogel contact lenses have an average equilibrium water content (EWC) of 30% to 70%, or an average oxygen permeability of at least 55 barrer when fully hydrated, or an average of from about 0.2 MPa to about 0.9 MPa when fully hydrated. Tensile modulus, or an average bubble trapping dynamic contact angle of less than 90 degrees upon full hydration, or an average bubble trap static contact angle of less than 70 degrees upon full hydration, or any combination thereof.

A batch of lenses can exhibit a change in average physical size when first tested shortly after manufacture and then tested again at subsequent time points. When multiple batches of lenses of the present disclosure are dimensionally stable, they can exhibit variations in the acceptable degree of average physical size. As used herein, the dimensional stability difference is understood to mean the physical size between the physical size value of the batch of lenses that was first tested shortly after its manufacture and the physical size of the batch of lenses that were tested again at subsequent time points. The difference. Subsequent time points may be, for example, at least 2 weeks after the initial time point and up to 7 years after the initial time point. The batch of polyoxyxahydrogel contact lenses have less than +/- 3% based on the average of the lens diameters of a representative number of lenses in the batch (eg, 20 lenses in the batch) (±3.0%) difference in average dimensional stability. For a batch of lenses, an average dimensional stability difference of less than +/- 3% (±3.0%) is considered a dimensionally stable batch, where the average dimensional stability difference is within one day of the manufacturing date of the batch of lenses. The initial time point is measured and at the second time point (wherein when the batch is stored at room temperature, the second time point is two to seven years after the initial time point; or when at a higher temperature (ie , in the accelerated shelf life test condition) when storing the batch, the second time point represents the difference between the physical size values of the batch at the time of storage at room temperature for two to seven years) . In one example, the accelerated shelf life test conditions, particularly useful for determining the difference in average dimensional stability, are maintained at 70 ° C for 4 weeks, although other time periods and other temperatures may be used. The average dimensional stability difference is the actual diameter ( _initial diameter) of the representative lens used for the first measurement and the actual diameter (diameter _final ) of the representative lens measured after storage at room temperature or under accelerated shelf life conditions, This is determined by averaging the individual dimensional stability differences for each representative lens. Representative lenses that are first measured and representative lenses that are measured after storage may be the same lens or may be different lenses. The difference in average dimensional stability used herein is expressed as a percentage (%). The individual dimensional stability differences were determined using the following equation (A): ((diameter _final - diameter _initial ) / diameter _initial ) x 100 (A).

On average, the change in diameter of the batch of polyoxyl hydrogel contact lenses is less than 3% (±3.0%) in either direction of the target value. As an example, if the contact lens has a target diameter (chord diameter) of 14.20 mm, the batch of polyoxyxam hydrogel contact lenses of the present invention will have an average diameter of 13.77 mm to 14.63 mm (the average of the population in the batch) value). In one example, the dimensional stability difference is less than +/- 2% (± 2.0%). As an example, if the contact lens has a target diameter (chord diameter) of 14.20 mm, the batch of polyoxyxam hydrogel contact lenses of the present invention will have an average diameter of 13.92 mm to 14.48 mm (the average of the population in the batch) value). Preferably, the average diameter of the batch of polyoxyhydrogel contact lenses does not vary by more than +/- 0.20 mm relative to the target diameter (typically 13.00 mm to 15.00 mm).

In the accelerated shelf life study, it can be determined that it has been at an elevated temperature (eg, above 40 ° C, including, for example, 50 ° C, or 55 ° C, or 65 ° C, or 70 ° C, or 80 ° C, or 95 ° C and Such as the difference in the average dimensional stability of contact lenses stored for a period of time. Alternatively, the average dimensional stability of a contact lens that has been stored for a period of time at room temperature (e.g., about 20-25 ° C) can be determined.

For accelerated shelf life studies, the following equation can be used to determine the number of months of storage at a particular temperature equivalent to the length of time required for storage at room temperature: required shelf life = [N x 2 ^y ] + n (B Where N = number of months of storage under accelerated conditions

2 ^y = acceleration factor

y=(test temperature -25°C)/10°C

n = lens age at the beginning of the study (in months) Based on this equation, the following storage time has been calculated: storage at 35 ° C for 6 months is equivalent to aging at 25 ° C for 1 year, storage at 45 ° C for 3 months is equivalent to aging at 25 ° C for 1 year, at 55 ° C Storage for 3 months corresponds to aging at 25 ° C for 2 years, and storage at 65 ° C for 3 months corresponds to aging at 25 ° C for 4 years.

The present disclosure also provides methods of making polyoxyxide hydrogel contact lenses. According to the teachings of the present invention, the method comprises providing a polymerizable composition. The polymerizable composition or contact lens formulation comprises a first oxoxane monomer represented by formula (1): Wherein m in the formula (1) represents an integer of 3 to 10, and n in the formula (1) represents an integer of 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each R ² in the formula (1) is independently a hydrogen atom or a methyl group. The polymerizable composition also comprises a second oxoxane monomer having a number average molecular weight greater than 7,000 Daltons. The total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts by weight to 50 unit parts by weight. The polymerizable composition also comprises at least one hydrophilic vinylguanamine monomer present in the polymerizable composition in an amount of from about 30 to about 60 unit parts by weight. The contact lens has an ophthalmically acceptable wettable lens surface when fully hydrated. Optionally, the polymerizable composition also comprises at least one third oxetane monomer, or at least one crosslinking agent, or at least one hydrophobic monomer, or any combination thereof.

The method can also include the step of polymerizing the polymerizable composition to form a polymeric lens body. The step of polymerizing the polymerizable composition can be carried out in a contact lens mold Implemented in the assembly. The polymerizable composition can be cast molded between molds formed from thermoplastic polymers. The thermoplastic polymer used to form the molding surface of the mold may comprise a polar polymer or may comprise a non-polar polymer. Alternatively, the polymerizable composition can be formed into a lens by various methods known to those skilled in the art, such as spin casting, injection molding, forming a polymeric rod and then turning to form a lens body or the like.

The method can also include contacting the polymeric lens body with a wash liquor to remove the extractable material, such as unreacted monomers, uncrosslinked materials that are not physically fixed in the polymeric lens body, diluents, and the like. The washing liquid may be a liquid containing no volatile organic solvent, or may contain a volatile organic solvent (for example, a solution which may be a volatile organic solvent or a volatile organic solvent).

In accordance with the present disclosure, a polymeric lens body can be packaged in a contact lens package (eg, a blister pack or glass vial) with a contact lens packaging solution. After packaging, the package can be sealed and the polymeric lens body and contact lens packaging solution sterilized by, for example, autoclaving the sealed package to produce a polyoxyxahydrogel contact lens product.

The method of the present invention can further comprise repeating the steps to produce a plurality of polyoxyxahydrogel contact lenses.

In any of the methods of the present invention, a specific first oxetane monomer, such as a monomer represented by formula (1), wherein m is 4, in formula (1), may be provided in the polymerizable composition. In the formula (1), R ¹ is a butyl group in the formula (1), and each of R ² in the formula (1) is independently a hydrogen atom or a methyl group.

In any of the methods of the present invention, the second oxane monomer or, optionally, at least one third oxane monomer can be represented by formula (2): Wherein R ₁ in the formula (2) is selected from a hydrogen atom or a methyl group; R ₂ in the formula (2) is selected from hydrogen or a hydrocarbon group having 1 to 4 carbon atoms; and m in the formula (2) represents 0 to 10 An integer of the formula (2) represents an integer from 4 to 100; a and b represent an integer of 1 or more; a+b is equal to 20 to 500; b/(a+b) is equal to 0.01 to 0.22; The configuration of the oxyalkyl unit includes a random configuration. As an example, the oxoxane monomer can be represented by the formula (2), wherein m in the formula (2) is 0, n in the formula (2) is an integer of 5 to 15, and a is an integer of 65 to 90. And b is an integer of 1 to 10, and R ₁ in the formula (2) is a methyl group, and R ₂ in the formula (2) is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

In the process of the present invention, the step of contacting the polymeric lens body with the wash liquor is understood to be an extraction step because the extractable material can be removed from the polymeric lens body during the process. When the washing liquid contains water or an aqueous solution containing no volatile organic solvent, the contacting step can be understood as both an extraction step and a hydration step. In another example of the method, the contacting step can comprise contacting the polymeric lens body with a wash liquid comprising a volatile organic solvent (eg, a liquid containing a primary alcohol (eg, methanol, ethanol, n-propanol, and the like). Some wash liquors may contain secondary alcohols such as isopropyl alcohol and the like. The use of a washing liquid containing one or more volatile organic solvents can aid in the removal of the hydrophobic material from the polymerized lens body, and thereby the resulting polyoxyxahydrogel contact lens can be improved Humidity. These methods are understood to be extraction steps based on volatile organic solvents. In other methods, the contacting step comprises contacting the polymeric lens body with an aqueous wash liquid that is free of volatile organic solvents. These methods are understood to be a completely aqueous washing step because the volatile organic solvent is not included in the washing liquid. Water-based washing solutions useful in such processes include water (eg, deionized water), saline solutions, buffer solutions, or aqueous solutions containing surfactants or other non-volatile ingredients, such other non-volatile ingredients. The hydrophobic component can be modified to improve the self-polymerizing contact lens body as compared to the use of only deionized water, or the deformation of the polymeric contact lens body can be reduced.

After washing, the contact lens can be placed in a package (eg, a plastic blister pack) containing a packaging solution (eg, a buffered saline solution), which may or may not contain a surfactant, an anti-inflammatory agent, an antimicrobial agent, Contact lens wetting agents and the like; and can be sealed and sterilized. The packaging solution for packaging the polyoxyxahydrogel contact lenses of the present disclosure may comprise a wetting agent to increase the wettability of the lens surface. However, it will be understood that the lens surface of the polyoxyxahydrogel contact lens of the present disclosure has an ophthalmically acceptable wettable surface prior to contact with a packaging solution comprising a wetting agent and is wetted in the packaging solution. The agent merely improves the wettability of the ophthalmically acceptable wettable surface and therefore does not require the provision of an ophthalmically acceptable wettable surface to the contact lens.

Instance

The following examples 1-25 illustrate certain aspects and advantages of the invention, which should not be construed as limiting.

As can be readily determined by reading the examples below, all example formulations are Contains no organic solvents. At the same time, all of the example formulations contained no N,N-dimethyl decylamine (DMA). Additionally, all of the example formulations below are free of polymeric wetting agents. In addition, all of the example formulations comprise at least one hydrophilic guanamine monomer having one N-vinyl group. Most of the example formulations (Examples 4-5, 8-13, 15 and 17-25) comprise a second oxane having a number average molecular weight greater than 7,000 Daltons.

The following chemicals are mentioned in Examples 1-25 and may be referred to by their abbreviations.

Si1: 2-methyl-2-[3-(9-butyl-1,1,3,3,5,5,7,7,9,9-decamethylpentaoxane-1) -yl)propoxy]ethyl ester (CAS number 1052075-57-6). (Si1 is available from Shin-Etsu Chemical Co., Ltd., Tokyo, Japan under product number X-22-1622).

Si2: α,ω-bis(methacryloxypropyl)-poly(dimethyloxane)-poly(ω-methoxy-poly(ethylene glycol)propylmethyloxane) (The synthesis of this compound can be carried out as described in US 20090234089, which is incorporated herein by reference)

Si3: methacryloxypropyl-terminated poly(dimethyloxane) (CAS number 58130-03-3; DMS-R18, available from Gelest)

VMA: N-vinyl-N-methylacetamide (CAS No. 003195786)

DMA: N,N-dimethyl methacrylate (CAS No. 2680-03-7)

HEMA: 2-hydroxyethyl methacrylate (CAS number 868-77-9)

HOB: 2-hydroxybutyl methacrylate (CAS No. 29008-35-3)

EGMA: ethylene glycol methyl ether methacrylate (CAS number 6976-93-8)

MMA: Methyl methacrylate (CAS No. 80-62-6)

EGDMA: ethylene glycol dimethacrylate (CAS No. 97-90-5)

TEGDMA: Triethylene glycol dimethacrylate (CAS No. 109-16-0)

BVE: 1,4-butanediol vinyl ether (CAS No. 17832-28-9)

DEGVE: Diethylene glycol vinyl ether (CAS number 929-37-3)

EGVE: ethylene glycol vinyl ether (CAS No. 764-48-7)

TEGDVE: Triethylene glycol divinyl ether (CAS number 765-12-8)

AE: 2-allyloxyethanol (CAS No. 111-45-5)

V-64: 2,2'-azobis-2-methylpropanoid (CAS No. 78-67-1)

UV1: 2-(4-Benzylmercapto-3-hydroxyphenoxy)ethyl acrylate (CAS No. 16432-81-8)

UV2: 2-(3-(2H-benzotriazol-2-yl)-4-hydroxy-phenyl)ethyl methacrylate (CAS No. 96478-09-0)

RBT1: 1,4-bis[4-(2-methylpropenyloxyethyl)phenylamino]anthracene (CAS No. 121888-69-5)

RBT2: 1,4-bis[(2-hydroxyethyl)amino]-9,10-nonanedione bis(2-acrylic acid) ester (CAS registration number 109561071)

TPP: triphenylphosphine (CAS No. 603-35-0)

pTPP: polymerizable TPP: diphenyl (p-vinylphenyl) phosphine (CAS No. 40538-11-2)

Polyoxyl hydrogel contact lens manufacturing and testing procedures

For each example, the chemical compounds described in Examples 1-25 were weighed out in amounts corresponding to the unit parts and combined to form a mixture. Will mix The material was filtered into a vial via a 0.2-5.0 micron syringe filter. Store the mixture for up to about 2 weeks. A mixture is understood to be a polymerizable polyoxyxahydrogel contact lens precursor composition, or a polymerizable composition as used herein. In Examples 1-25, the amounts of the listed ingredients are given in parts by weight of the polymerizable composition.

A volume of the polymerizable composition is cast molded by placing the composition in contact with the lens defining surface of the female member. In all of the following Examples 1-25, the molding surface of the female mold member was formed of a non-polar resin, specifically polypropylene. The male member is placed in contact with the female member to form a contact lens mold assembly comprising a contact lens shaped cavity containing the polymerizable composition. In Examples 1-25 below, the molding surface of the male mold member was formed of a non-polar resin, specifically polypropylene.

The contact lens mold assembly is placed in a nitrogen rinse oven to render the polymerizable composition heat curable. For all of Examples 1-25, the contact lens mold assembly was exposed to a temperature of at least about 55 ° C for about 2 hours. Examples of curing conditions that can be used to cure the polyoxyxahydrogel contact lenses described herein include exposing the contact lens mold assembly to a temperature of 55 ° C for 40 minutes, exposing at 80 ° C for 40 minutes, and exposing at 100 ° C for 40 minutes. minute. Other contact lenses can be made using the same curing conditions, but without using a first temperature of 55 °C, which can be 65 °C.

After polymerizing the polymerizable composition to form a polymeric lens body contained in a mold assembly, the contact lens mold assembly is demolded to separate the male and female mold members. The polymeric lens body remains attached to the punch or die. A dry demolding method in which the mold assembly is not in contact with the liquid medium may be used, or a wet mold release method in which the mold assembly is brought into contact with a liquid medium (for example, water or an aqueous solution) may be used. law. Mechanical dry demolding methods may involve applying a mechanical force to one or both of the mold members to separate the mold members. In all of the following Examples 1-25, a dry demolding method was used.

The polymeric lens body is then delensed from the male or female mold to produce a delensed polymeric lens body. In one example of the delensing method, the dry lens method can be used to defoam the polymeric lens body from the male mold member by, for example, manually peeling the lens from the male mold member; or pressing the male mold member and introducing the gas To the male mold member and the polymeric lens body, the dry polymeric lens body is lifted from the male mold member by a vacuum device and the male mold member is discarded. In other methods, the polymeric lens body can be delensed using a wet delensing method by contacting the dried polymeric lens body with a liquid release medium, such as water or an aqueous solution. For example, the male mold member to which the polymeric lens body is attached can be immersed in a container containing the liquid until the polymeric lens body is separated from the male mold member. Alternatively, a volume of liquid release medium can be added to the female mold to soak the polymeric lens body in the liquid and separate the lens body from the female mold member. In the following Examples 1-25, a dry delensing method was used. After separation, the lens body can be manually lifted from the mold member using tweezers or using a vacuum device and placed in a tray.

The delensed lens product is then washed to remove the extractable material from the polymeric lens body and the product is hydrated. The extractable material includes a polymerizable component (eg, a monomer, or a crosslinking agent, or any optional polymerizable component (eg, a color former or a UV blocker), or a combination thereof) present in the polymerizable composition. It remains in unreacted form, partially reacted form, or uncrosslinked form, or any combination thereof after polymerization of the lens body and prior to extraction of the lens body In the polymeric lens body. The extractable material can also include any non-polymerizable component present in the polymerizable composition, such as any optional non-polymerizable colorant, or UV blocker, or diluent, or chain transfer agent, or any combination thereof. It remains in the polymeric lens body after polymerization of the polymeric lens body and prior to extraction of the polymeric lens body.

In other methods, such as those involving wet lens removal by contacting the mold and lens with a liquid release medium, volatile organic solvents (eg, lower alcohols such as methanol, ethanol, or any of them) may be used. A combined wash liquid washes the delensed polymerized contact lens body to remove the extractable component from the lens body. For example, by contacting the lens body with an aqueous washing liquid that does not contain a volatile organic solvent (eg, deionized water, or a surfactant solution, or a saline solution, or a buffer solution, or any combination thereof) The devitrified polymeric contact lens body is washed to remove the extractable component from the lens body. Washing can be carried out in the final contact lens package or can be carried out in a wash tray or wash tank.

In the following Examples 1-25, after the dry demolding and dry de-glassing steps, the dry lens-off lens body is placed in the cavity of the tray, and by contacting the polymeric lens body with one or more volumes of the extract To extract and hydrate the lens release polymeric lens body. The extraction and hydration fluids used in the extraction and hydration process consist of a) a combination of a volatile organic solvent-based extract and a volatile organic solvent-free hydration solution, or b) a volatile organic solvent-free extract. And hydration fluid, that is, completely based on water extraction and hydration fluid. Specifically, in the following Examples 1-5, the extraction and hydration process sequentially comprises at least two extraction steps carried out in separate parts of ethanol, at least one in Tween 80. 50: 50 wt/wt ethanol: an extraction step carried out in a portion of an aqueous solution, at least three extraction and hydration steps in a separate portion of a Tween 80 deionized aqueous solution, wherein each extraction step or extraction and hydration step lasts for about 5 Minutes to 3 hours. In Examples 6-25 below, the extraction and hydration process used included at least three extraction and hydration steps in a separate portion of the Tween 80 deionized water solution, wherein the temperature of the Tween 80 solution portion was between room temperature and about 90 °C. Within the range, and each of the extraction and hydration steps lasts from about 15 minutes to about 3 hours.

The washed, extracted and hydrated lenses are then individually placed in a contact lens blister pack containing a phosphate buffered saline packaging solution. The blister pack is sealed and sterilized by autoclaving.

After sterilization, the properties of the lens are determined as described herein, such as contact angle (including dynamic and static contact angles), oxygen permeability, ion current, modulus, elongation, tensile strength, water content, and the like.

For contact lenses of the present invention, the contact angle (including dynamic and static contact angles) can be determined using conventional methods known to those skilled in the art. For example, the contact angles and receding contact angles of the contact lenses provided herein can be measured using conventional drop shape methods such as the seat drop method or the bubble trap method.

In the following Examples 1-25, the Kruss DSA 100 instrument (Kruss GmbH, Hamburg) was used and the forward and reverse contact angles of the polyoxyl hydrogel contact lenses were determined as described in the following literature: DABrandreth: "Dynamic contact angles And contact angle hysteresis", Journal of Colloid and Interface Science, Vol. 62, 1977, pp. 205-212; and R. Knapikowski, M. Kudra: "Kontaktwinkelmessungen nach dem Wilhelmy-Prinzip-Ein statistischer Ansatz zur Fehierbeurteilung", Chem. Technik, Vol. 45, 1993, pp. 179-185; and U.S. Patent No. 6,436, 481, incorporated herein by reference.

As an example, the advancing contact angle and the receding contact angle were measured by a bubble trap method using phosphate buffered saline (PBS; pH = 7.2). The lenses were placed flat on the quartz surface before testing and rehydrated with PBS for at least 10 minutes. Air bubbles are placed on the surface of the lens using an automatic injection system. The size of the air bubble is increased and decreased to obtain a receding angle (a steady state obtained when the bubble size is increased) and an advancing angle (a steady state obtained when the bubble size is reduced).

The modulus, elongation and tensile strength values of the lenses of the present invention can be determined using conventional methods known to those skilled in the art, for example, according to the test method of ANSI Z80.20. The modulus, elongation, and tensile strength values reported herein were determined using Instron Model 3342 or Model 3343 mechanical test systems (Instron, Inc., Norwood, MA, USA) and Bluehill Materials test software using custom rectangular shapes. Contact lenses are cut to prepare a rectangular sample strip. Modulus, elongation and tensile strength were measured in a chamber with a relative humidity of at least 70%. The lenses to be tested were soaked in phosphate buffered saline (PBS) for at least 10 minutes prior to testing. The center strip of the cut lens is cut using a die while holding the lens on the concave side. The thickness of the strip was measured using a calibration gauge (Rehder Electronic Thickness Gauge, Rehder Development, Castro Valley, CA, USA). The strip was loaded into a fixture of a calibrated Instron device using tweezers and the strip was assembled on at least 75% of the fixture surface of each fixture. Execution is designed to measure maximum Test method for the average and standard deviation of load (N), tensile strength (MPa), strain at maximum load (% elongation), and tensile modulus (MPa), and the results were recorded.

The percent energy loss of the polyoxyxahydrogel contact lenses of the present invention can be determined using conventional methods known to those skilled in the art. For the following Examples 1-25, the energy loss percentage was calculated using an Instron Model 3343 (Instron Corporation, Norwood, MA, USA) mechanical test system using a 10N force transducer (Instron Model 2519-101) and Bluehill Materials test software (including the TestProfiler module). ) to determine. The energy loss is measured in a room where the relative humidity is at least 70%. Each lens was soaked in phosphate buffered saline (PBS) for at least 10 minutes prior to testing. The lenses are loaded into the fixture of the calibrated Instron device using tweezers, and the lenses are mounted vertically symmetrically between the clamps as much as possible so that the lenses fit over at least 75% of the fixture surface of each clamp. A test designed to determine the energy required to stretch the lens to 100% strain at a rate of 50 mm/min and then restore it to 0% strain was then performed on the lens. Only one test was performed on a single lens. Once the test is complete, the energy loss is calculated using the following equation: energy lost (%) = (energy reaching 100% strain - energy recovering 0% strain) / energy reaching 100% strain x 100%.

The ion current of the lenses of the present invention can be determined using conventional methods known to those skilled in the art. For the lenses of Examples 1-25 below, the ion current system is measured using a technique substantially similar to the "ion flow technique" described in U.S. Patent 5,849,811, the disclosure of which is incorporated herein by reference. The hydrated lenses were allowed to equilibrate in deionized water for at least 10 minutes prior to measurement. Will measure The lens is placed between the convex and concave portions in the lens holding device. The convex and concave portions include a flexible sealing ring between the lens and the respective convex or concave portions. After the lens is placed in the lens holding device, the lens holding device is then placed in the screw cap. The lid is screwed onto the glass tube to define the supply chamber. The supply chamber was filled with 16 ml of 0.1 M NaCl solution. The receiving chamber was filled with 80 ml of deionized water. The lead of the conductivity meter is immersed in deionized water in the receiving chamber and a stir bar is added to the receiving chamber. The receiving chamber was placed in a water bath and the temperature was maintained at about 35 °C. Finally, the supply chamber is immersed in the receiving chamber to level the NaCl solution in the supply chamber with the receiving chamber. Once the temperature in the receiving chamber is equilibrated to 35 ° C, the conductivity is measured every 2 minutes for at least 10 minutes. The conductivity versus time data is substantially linear and the data is used to calculate the ion current value of the tested lens.

The oxygen permeability (Dk) of the lenses of the present invention can be determined using conventional methods known to those skilled in the art. For example, the Dk value can be determined using a commercially available instrument of the MOCON® Ox-Tran system (Mocon Corporation, Minneapolis, MN, USA), for example using the Mocon method, as described in U.S. Patent No. 5,817,924. The patent is incorporated herein by reference. The Dk values of the lenses in Examples 1-25 below were determined using the method described in Chhabra et al. (2007), A single-lens polarographic measurement of oxygen permeability (Dk) for hypertransmissible soft contact lenses. Biomaterials 28: 4331-4342. , which is incorporated herein by reference.

The equilibrium water content (EWC) of the lenses of the present invention can be determined using conventional methods known to those skilled in the art. For the lenses of Examples 1-25 below, The hydrated polyoxyhydrogel hydrogel contact lens is removed from the aqueous liquid, wiped to remove excess surface water and weighed. The weighed lenses can then be dried in an oven at 80 ° C under vacuum and the dried lenses are then weighed. The weight difference is determined by subtracting the weight of the dried lens from the weight of the hydrated lens. The water content (%) is (weight difference / hydration weight) × 100.

The percentage of wet extractable components or dry extractable components in the lens can be determined by extraction of the lens in an organic solvent that does not dissolve the polymeric lens body, according to methods known to those skilled in the art. For the lenses of Examples 1-25 below, extraction was carried out in methanol using a Sohxlet extraction method. For the determination of wet extractable components, samples of fully hydrated and sterilized contact lenses were prepared by removing excess packaging solution from each lens and drying it in a vacuum oven at 80 ° C overnight (eg, at least 5 per batch) lens). For the determination of the dry extractable component, a sample of the polymeric lens body that was not washed, extracted, hydrated or sterilized was prepared by drying the lens body in a vacuum oven at 80 ° C overnight. Upon drying and cooling, each lens was weighed to determine its initial dry weight (W1). Each lens is then placed in a porous stackable Teflon sleeve and the sleeves are stacked to form an extraction column with an empty cannula placed on top of the column. The extraction column was placed in a small Sohxlet extractor attached to a condenser and a round bottom flask containing 70-80 ml of methanol. The water is circulated through the condenser and the methanol is heated until it is gently boiled. The lens was extracted for at least 4 hours from the moment the first condensation of methanol occurred. The extracted lenses were again dried overnight in a vacuum oven at 80 °C. Upon drying and cooling, each lens was weighed to obtain the dry weight (W2) of the extracted lens, and the following calculation was performed on each lens to determine the percentage of the wet extractable component: [(W1-W2)/W1 ] × 100.

Example 1

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested, and the washing method uses a washing liquid containing a volatile organic solvent-based extract and a hydration liquid composed of a liquid containing no volatile organic solvent. The contact lenses comprise units derived from two oxoxane monomers Si1 and Si3 and a hydrophilic monomer VMA. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, the batch of polyoxyl hydrogel contact lenses have an average EWC of 30% wt/wt to 70% wt/wt when fully tested at the beginning of the shelf life study and are stored at 95 °C. There was an average dimensional stability difference of less than ±3.0% after 22 days.

Example 2

Mixing and filtering the following chemical compounds in the specified amounts by using the procedure described in the Polymethacrylate Hydrogel Contact Lens Manufacturing and Testing Procedures given above A DEK polymerizable composition.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested, and the washing method uses a washing liquid containing a volatile organic solvent-based extract and a hydration liquid composed of a liquid containing no volatile organic solvent. The contact lenses comprise units derived from two oxoxane monomers Si1 and Si3 and a hydrophilic monomer VMA. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, at the beginning of the shelf life study, the lenses had an EWC of 52% wt/wt, a modulus of 0.63 MPa, and an ion current of 3.62 (×10 ^-3 mm ² /min) when fully hydrated. And having an average dimensional stability difference of less than ±3.0% after storage for 20 days at 95 °C.

Example 3

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested, and the washing method uses a washing liquid containing a volatile organic solvent-based extract and a hydration liquid composed of a liquid containing no volatile organic solvent. The contact lenses comprise units derived from two oxoxane monomers Si1 and Si3 and a hydrophilic monomer VMA. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, the polyoxyxane hydrogel contact lenses have an EWC of about 52% wt/wt, a modulus of about 0.58 MPa, and about 0.67% wet extractable when fully hydrated when tested at the beginning of the shelf life study. The content, a static bubble contact angle of about 30 degrees, and a bubble advance dynamic contact angle of about 50.1 degrees, and an average dimensional stability difference of less than ± 3.0% after storage for 22 days at 95 °C.

Example 4

Mixing and filtering the following chemical compounds in the specified amounts by using the procedure described in the Polymethacrylate Hydrogel Contact Lens Manufacturing and Testing Procedures given above A DEK polymerizable composition.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested, and the washing method uses a washing liquid containing a volatile organic solvent-based extract and a hydration liquid composed of a liquid containing no volatile organic solvent. The contact lenses comprise units derived from two oxoxane monomers Si1 and Si2 and a hydrophilic monomer VMA. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, the polyoxyxahydrogel contact lenses have an EWC of 53% wt/wt to 54% wt/wt, a modulus of about 0.43 MPa, and about 1.23 when fully hydrated when tested at the beginning of the shelf life study. %wt/wt wet extractable content, about 38 degrees of bubble trapping static contact angle, about 50.0 degrees of bubble trapping dynamic advancing contact angle, 2.5-3.0 (×10 ^-3 mm ² /min) ion current, 70 barrer Dk, elongation of about 450%, tensile strength of 1.40 MPa, percentage of transmittance of 98%, energy loss of 36%, and swelling factor of about 21%, and less than ± after storage for 20 days at 95 ° C 3.0% Average Dimensional Stability Difference The polymeric lens body had a dry extractable content of about 17% wt/wt when tested prior to extraction and hydration.

Example 5

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested, and the washing method uses a washing liquid containing a volatile organic solvent-based extract and a hydration liquid composed of a liquid containing no volatile organic solvent. The contact lenses comprise units derived from two oxoxane monomers Si1 and Si2 and a hydrophilic monomer VMA. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, these polyoxyxahydrogel contact lenses have an oxygen permeability of greater than 60 barrer, an EWC of about 53% wt/wt, and about 2.90 (×10 ^-3) when fully hydrated when tested at the beginning of the shelf life study. Ign flow of mm ² /min), modulus of about 0.40 MPa, elongation of about 425%, tensile strength of about 1.4 MPa, static bubble trapping angle of about 37 degrees, dynamic bubble trap of about 48 to 52 degrees Advancing contact angle, about 98% transmittance, about 1.30% wt/wt wet extractable content, about 35% to about 36% energy loss, and 21% about swelling factor, and stored at 80 ° C at least After 2 weeks there was an average dimensional stability difference of less than +/- 3.0%.

Example 6

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise a single sample derived from a mixture of two oxoxane monomers Si1 and Si3 and hydrophilic monomers VMA and BVE. yuan. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, these polyoxyxahydrogel contact lenses have an EWC of about 55% wt/wt and an ion of about 3.1 (×10 ^-3 mm ² /min) when fully hydrated when tested at the beginning of the shelf life study. Flow, Dk of about 72 barrer, modulus of about 0.70 MPa, elongation of about 345%, tensile strength of about 2.4 MPa, water rupture time of more than 20 seconds, wet extractable component of about 3.9% wt/wt, And about 40% energy loss, and having an average dimensional stability difference of less than +/- 3.0% after storage for more than 2 weeks at 80 °C. The polymeric lens body had about 11% wt/wt dry extractable components when tested prior to extraction and hydration.

Example 7

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and Prepared and tested by a washing method using an extract containing no volatile organic solvent The composition of the extraction and hydration solution. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from two oxoxane monomers Si1 and Si3 and a hydrophilic monomer VMA. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, these polyoxyxahydrogel contact lenses have an EWC of about 58% wt/wt and an ion of about 4.14 (×10 ^-3 mm ² /min) when fully hydrated when tested at the beginning of the shelf life study. Flow, modulus of about 0.77 MPa, elongation of about 349%, tensile strength of about 1.75 MPa, water rupture time of more than 20 seconds, wet extractable content of about 4.42% wt/wt, and energy of about 41% Loss, and having an average dimensional stability difference of less than +/- 3.0% after storage for at least 2 weeks at 80 °C.

Example 8

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

a batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedures described in the manufacturing and testing procedures for polyoxyl hydrogel contact lenses and The test method is prepared and tested by a dry release method, a dry delensing method, and a washing method using an extraction and hydration liquid composed of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from a mixture of two oxoxane monomers Si1 and Si2 and hydrophilic monomers VMA and BVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, these polyoxyxahydrogel contact lenses have an EWC of about 55% wt/wt and an ion of about 4.19 (×10 ^-3 mm ² /min) when fully hydrated when tested at the beginning of the shelf life study. Flow, modulus of about 0.61 MPa, elongation of about 275%, tensile strength of about 1.51 MPa, water rupture time of greater than 20 seconds, and wet extractable component of about 4.10% wt/wt, and at 80 ° C The lower than 2 weeks or more has an average dimensional stability difference of less than +/- 3.0%.

Example 9

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

One batch of polyoxygenated hydrogel contact lenses is used according to this formulation The manufacturing procedure and test method described in the manufacturing and testing procedures for the hydrogel contact lens are prepared and tested by a dry demolding method, a dry delensing method and a washing method using an extract containing no volatile organic solvent. Extraction and hydration of liquid composition. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from a mixture of two oxoxane monomers Si1 and Si2 and hydrophilic monomers VMA and BVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, these polyoxyxahydrogel contact lenses have an EWC of about 58% wt/wt and an ion of about 2.75 (×10 ^-3 mm ² /min) when fully hydrated when tested at the beginning of the shelf life study. Flow, modulus of about 0.66 MPa, elongation of about 216%, tensile strength of about 0.87 MPa, water rupture time of more than 20 seconds, and wet extractable component of about 4.56% wt/wt, and at 95 ° C There is a difference in average dimensional stability of less than +/- 3.0% after 6 days of storage.

Example 10

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from a mixture of two oxoxane monomers Si1 and Si2 and hydrophilic monomers VMA and BVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, these polyoxyxahydrogel contact lenses have an EWC of about 56% wt/wt and an ion of about 3.54 (×10 ^-3 mm ² /min) when fully hydrated when tested at the beginning of the shelf life study. Flow, modulus of about 0.57 MPa, elongation of about 310%, tensile strength of about 1.90 MPa, water rupture time of more than 20 seconds, wet extractable component of about 4.74% wt/wt, and about 34% to 36% energy loss and an average dimensional stability difference of less than +/- 3.0% after 7 days storage at 80 °C. The polymeric lens body had about 14.39% wt/wt dry extractable components when tested prior to extraction and hydration.

Example 11

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from a mixture of two oxoxane monomers Si1 and Si2 and hydrophilic monomers VMA and BVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, these polyoxyxahydrogel contact lenses have an EWC of about 57% wt/wt and an ion of about 3.68 (×10 ^-3 mm ² /min) when fully hydrated when tested at the beginning of the shelf life study. Flow, modulus of about 0.69 MPa, elongation of about 314%, tensile strength of about 1.30 MPa, water rupture time of more than 20 seconds, wet extractable component of about 1.81% wt/wt, and about 34% Energy loss, and having an average dimensional stability difference of less than +/- 3.0% after storage for 14 days at 80 °C.

Example 12

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from a mixture of three oxoxane monomers Si1, Si2 and Si3 and hydrophilic monomers VMA and BVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, the polyoxyxahydrogel contact lenses have an EWC of about 55% wt/wt and an ion of about 3.06 (×10 ^-3 mm ² /min) when fully hydrated when tested at the beginning of the shelf life study. Flow, modulus of about 0.85 MPa, elongation of about 284%, tensile strength of about 1.88 MPa, water rupture time of greater than 20 seconds, wet extractable component of about 2.38% wt/wt, and about 36% Energy loss, and having an average dimensional stability difference of less than +/- 3.0% after storage for 14 days at 80 °C.

Example 13

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from a mixture of two oxoxane monomers Si1 and Si2 and hydrophilic monomers VMA and BVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, these polyoxyxahydrogel contact lenses have an EWC of about 54% wt/wt and an ion of about 3.57 (×10 ^-3 mm ² /min) when fully hydrated when tested at the beginning of the shelf life study. Flow, modulus of about 0.66 MPa, elongation of about 274%, tensile strength of about 1.40 MPa, and wet extractable content of about 3.8% wt/wt, and less than +/ after storage for 7 days at 80 °C - 3.0% difference in average dimensional stability.

Example 14

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from a mixture of three oxoxane monomers Si1, Si2 and Si3 and hydrophilic monomers VMA and BVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, when tested at the beginning of the shelf life study, the polyoxyxahydrogel contact lenses have a modulus of about 0.81 MPa, an elongation of about 351%, a tensile strength of about 1.61 MPa, and EWC from 30% wt/wt to 70% wt/wt, and having an average dimensional stability difference of less than +/- 3.0% at 80 °C for 14 days.

Example 15

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from a mixture of three oxoxane monomers Si1, Si2 and Si3 and hydrophilic monomers VMA and BVE. This batch of contact lenses has ophthalmically acceptable wettable lenses surface.

In addition, when tested at the beginning of the shelf life study, the polyoxyxahydrogel contact lenses have an ion current of about 3.33 (×10 ^-3 mm ² /min), a modulus of about 0.74 MPa, when fully hydrated, And about 222% elongation, and having an average dimensional stability difference of less than +/- 3.0% for 14 days at 80 °C.

Example 16

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from a mixture of two oxoxane monomers Si1 and Si3 and hydrophilic monomers VMA and BVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, when tested at the beginning of the shelf life study, the polyoxyxahydrogel contact lenses have an EWC of about 57% wt/wt, a modulus of about 0.70 MPa, and an energy loss of about 40% when fully hydrated. And a foaming dynamic advancing contact angle of from about 50 to about 60 degrees and an average dimensional stability difference of less than +/- 3.0% at 80 °C for 14 days.

Example 17

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise a single sample derived from a mixture of two oxoxane monomers Si1 and Si2 and hydrophilic monomers VMA and BVE. yuan. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, the polyoxyxahydrogel contact lenses have an EWC of about 56% wt/wt, a modulus of about 0.50 MPa, and about 47 to about 51 degrees when fully hydrated when tested at the beginning of the shelf life study. The bubble trapping dynamically advances the contact angle and has an average dimensional stability difference of less than +/- 3.0% at 440 °C for 4.4 weeks.

Example 18

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. These contact lenses are derived from two types of enamel A unit of a mixture of oxyalkylene monomers Si1 and Si2 and hydrophilic monomers VMA and BVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

Additionally, the polyoxyxahydrogel contact lenses have an EWC of about 55% wt/wt, a modulus of about 0.60 MPa, and about 47 to about 55 degrees when fully hydrated when tested at the beginning of the shelf life study. The bubble trap dynamically advances the contact angle and has an average dimensional stability difference of less than +/- 3.0% after storage for 2 weeks at 80 °C.

Example 19

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. This batch of lenses is not violent during its manufacture Exposed to volatile organic solvents. The contact lenses comprise units derived from a mixture of two oxoxane monomers Si1 and Si2 and a hydrophilic monomer VMA and DEGVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

Additionally, the polyoxyxahydrogel contact lenses have an EWC of about 55% wt/wt to about 56% wt/wt, a modulus of about 0.71 MPa, when fully tested, at the beginning of the shelf life study. And a bubble-catching dynamic advancing contact angle of from about 45 to about 47 degrees and having an average dimensional stability difference of less than +/- 3.0% for at least 2 weeks at 80 °C.

Example 20

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. This batch of lenses is not exposed during its manufacture In volatile organic solvents. The contact lenses comprise units derived from a mixture of two oxoxane monomers Si1 and Si2 and a hydrophilic monomer VMA and EGVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, these polyoxyxahydrogel contact lenses have an EWC of about 56% wt/wt and a modulus of about 0.65 MPa when fully hydrated at the beginning of the shelf life study, and continue at 80 °C. 2 weeks have an average dimensional stability difference of less than +/- 3.0%.

Example 21

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. These contact lenses are derived from two types of enamel A unit of a mixture of oxyalkylene monomers Si1 and Si2 and a hydrophilic monomer, VMA and HEMA. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, the polyoxyxahydrogel contact lenses have an EWC of about 55% wt/wt to about 56% wt/wt, a modulus of about 0.53 MPa, when fully hydrated, when tested at the beginning of the shelf life study. A foaming dynamic advance contact angle of about 51 to about 53 degrees, and an energy loss of about 34%, and a flat dimensional stability difference of less than +/- 3.0% at 440 °C for 4.4 weeks.

Example 22

The polymerizable polyoxynoxy composition is obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the polyoxyl hydrogel contact lens manufacturing and testing procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and Prepared and tested by a washing method using an extract group containing no volatile organic solvent It is extracted and hydrated. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from a mixture of two oxoxane monomers Si1 and Si2 and a hydrophilic monomer VMA and DEGVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, these polyoxyxahydrogel contact lenses have an EWC of 57% wt/wt to 58% wt/wt, about 2.9 (×10 ^-3 mm ^{2 )} when fully hydrated when tested at the beginning of the shelf life study. /min) ion current, modulus of about 0.7 MPa, elongation of about 300%, tensile strength of about 1.5 MPa, dynamic advance contact angle of about 44 to about 48 degrees, about 5.10% wt/wt The wet extractable component, and an energy loss of from about 32% to about 33%, has an average dimensional stability difference of less than +/- 3.0% after storage for 4.4 weeks at 80 °C. The polymeric lens body had a dry extractable fraction of about 12.2% wt/wt when tested prior to extraction and hydration.

Example 23

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from a mixture of two oxoxane monomers Si1 and Si2 and hydrophilic monomers VMA and HOB. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, the polyoxyxahydrogel contact lenses have an EWC of about 55% wt/wt to about 56% wt/wt, about 4.1 (×10 ^-3) when fully hydrated when tested at the beginning of the shelf life study. Ign flow of mm ² /min), modulus of about 0.6 MPa, elongation of about 275%, tensile strength of about 1.2 MPa, dynamic advance contact angle of about 55 to about 58 degrees, about 4.6% wt/ The wet extractable component of wt, about 31% to about 32% energy loss, and about 27% swelling factor, has an average dimensional stability difference of less than +/- 3.0% after storage for 4.4 weeks at 80 °C. The polymeric lens body had a dry extractable component of about 10.6% wt/wt when tested prior to extraction and hydration.

Example 24

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from a mixture of two oxoxane monomers Si1 and Si2 and hydrophilic monomers VMA, BVE and DEGVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, these polyoxyxahydrogel contact lenses have an EWC of about 61% wt/wt and an ion of about 3.8 (×10 ^-3 mm ² /min) when fully hydrated when tested at the beginning of the shelf life study. Flow, modulus of about 0.5 MPa, elongation of about 279%, tensile strength of about 1.2 MPa, dynamic advance contact angle of about 45 to about 47 degrees, wet extractable component of about 4.55% wt/wt And about 30% to about 33% energy loss, and having an average dimensional stability difference of less than +/- 3.0% after storage for 14 days at 80 °C. The polymeric lens body had a dry extractable component of about 13.65% wt/wt when tested prior to extraction and hydration.

Example 25

The polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts using the procedures described in the Polyoxyl Hydrogel Contact Lens Manufacturing and Testing Procedures given above.

A batch of polyoxygenated hydrogel contact lenses using the formulation according to the manufacturing procedure and test method described in the manufacturing and testing procedures of the polyoxyxahydrogel contact lens, utilizing a dry release method, a dry release lens method, and The washing method is prepared and tested using an extraction and hydration solution consisting of an extract containing no volatile organic solvent. The lenses of this batch are not exposed to volatile organic solvents during their manufacture. The contact lenses comprise units derived from a mixture of two oxoxane monomers Si1 and Si2 and hydrophilic monomers VMA and BVE. This batch of contact lenses has an ophthalmically acceptable wettable lens surface.

In addition, the polyoxyxahydrogel contact lenses have an EWC of about 55% wt/wt to about 57% wt/wt, about 3.6 (×10 ^-3) when fully hydrated when tested at the beginning of the shelf life study. Ign flow of mm ² /min), modulus of about 0.7 MPa, elongation of about 285%, tensile strength of about 1.3 MPa, dynamic advance contact angle of about 47 to about 53 degrees, about 4.10% wt/ The wet extractable component of wt, and an energy loss of from about 34% to about 35%, has an average dimensional stability difference of less than +/- 3.0% after storage for 14 days at 80 °C. Upon testing and hydration testing, the polymeric lens body was found to have about 9.80% wt/wt dry extractable components.

Although the disclosure herein refers to certain illustrated embodiments, it is understood that the embodiments are presented by way of example and not limitation. The exemplifications of the present invention are to be construed as being limited by the scope of the present invention as defined by the other disclosures. .

A number of publications and patents are cited above. Each of the publications and patents cited is hereby incorporated by reference in its entirety.

Claims (15)

A polyoxyxahydrogel contact lens comprising: a polymeric lens body, which is a reaction product of a miscible polymerizable composition, the polymerizable composition comprising (a) a first oxygen represented by formula (1) Alkane monomer: Wherein m in the formula (1) represents an integer of from 3 to 10, n in the formula (1) represents an integer of from 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each R ² in the formula (1) is independently a hydrogen atom or a methyl group, the first siloxane monomer having a number average molecular weight of from 400 to 700 Daltons; (b) a second enthalpy; An oxane monomer having a number average molecular weight greater than 7,000 Daltons, wherein the total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts by weight to 50 unit parts by weight, and c) at least one hydrophilic guanamine monomer having an N-vinyl group, the hydrophilic guanamine single system being present in the polymerizable composition in an amount of from 30 unit parts by weight to 60 unit parts by weight; wherein the invisible form The lens has an ophthalmically acceptable wettable lens surface when fully hydrated. The contact lens of claim 1, wherein the polymerizable composition used to form the polymeric lens body does not contain an internal wetting agent, or is used to form When the polymerizable composition of the polymeric lens body is free of organic diluent, or when the lens is washed in a liquid containing no volatile organic solvent, or when the lens is not subjected to surface plasma treatment, or any combination thereof The contact lens has an ophthalmically acceptable wettable surface. The contact lens of claim 1 or 2, wherein the contact lens has an equilibrium water content (EWC) of 30% to 70% when fully hydrated. The contact lens of claim 1 or 2, wherein the polymeric lens has a bubble-catching dynamic advancing contact angle of less than 70 degrees when fully hydrated. The contact lens of claim 1 or 2, wherein the polymerizable composition is substantially free of N,N-dimethyl acrylamide (DMA). The contact lens of claim 1 or 2, wherein the first oxoxane monomer and the second oxane single system are present in the ratio of from about 2:1 to about 10:1, based on the unit parts In the polymeric composition. The contact lens of claim 1 or 2, wherein in the first oxane monomer, m in the formula (1) is 4, n in the formula (1) is 1, and R ¹ in the formula (1) It is a butyl group, and each R ² in the formula (1) is independently a hydrogen atom or a methyl group. The contact lens of claim 1 or 2, wherein the second oxane single system is represented by the formula (2): Wherein R ₁ in the formula (2) is selected from a hydrogen atom or a methyl group; and R ₂ in the formula (2) is selected from a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; m in the formula (2) represents An integer from 0 to 10; n in the formula (2) represents an integer from 4 to 100; a and b represent an integer of 1 or more; a+b is equal to 20 to 500; b/(a+b) is equal to 0.01 to 0.22 And the configuration of the oxane unit includes a random configuration. The contact lens of claim 8, wherein in the second oxane monomer, m in the formula (2) is 0, and n in the formula (2) is an integer of 5 to 10, and the a is 65 to 90. One of the integers, b is an integer from 1 to 10, R ₁ in the formula (2) is a methyl group, and R ₂ in the formula (2) is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. A batch of polyoxyhydrogel contact lenses comprising a plurality of contact lenses of any of the preceding claims, wherein the batch is based on an average of values measured for at least 20 individual lenses in the batch Polyoxyl hydrogel contact lenses have an average equilibrium water content (EWC) of 30% to 70%, or an average oxygen permeability of at least 55 barrer when fully hydrated, or an average of from about 0.2 MPa to about 0.9 MPa when fully hydrated. Tensile modulus, or an average bubble trapping dynamic contact angle of less than 70 degrees upon full hydration, or an average bubble trap static contact angle of less than 55 degrees upon full hydration, or any combination thereof. A method of making a polyoxyxahydrogel contact lens comprising: providing a miscible polymerizable composition comprising (a) a first oxoxane monomer represented by formula (1): Wherein m in the formula (1) represents an integer of from 3 to 10, n in the formula (1) represents an integer of from 1 to 10, and R ¹ in the formula (1) is an alkyl group having 1 to 4 carbon atoms And each R ² in the formula (1) is independently a hydrogen atom or a methyl group, the first siloxane monomer having a number average molecular weight of from 400 to 700 Daltons; (b) a second enthalpy; An oxane monomer having a number average molecular weight greater than 7,000 Daltons; wherein the total amount of the oxoxane monomer present in the polymerizable composition is from 30 unit parts by weight to 50 unit parts by weight; c) at least one hydrophilic guanamine monomer having an N-vinyl group, the hydrophilic guanamine single system being present in the polymerizable composition in an amount of from 30 unit parts by weight to 60 unit parts by weight; Polymerizing the composition polymerized in a contact lens mold assembly to form a polymeric lens body; contacting the polymeric lens body with a wash liquid to remove the extractable material from the polymeric lens body; and packaging the polymeric lens body in a contact lens a contact lens packaging solution in a package; wherein the contact lens is ophthalmically acceptable when fully hydrated Surface of the lens. The method of claim 11, further comprising the step of autoclaving the contact lens package to sterilize the polymeric lens body and the contact lens packaging solution. The method of any one of claims 11 to 12, wherein the polymerizing step comprises polymerizing the polymerizable composition in a contact lens mold assembly having a molding surface formed of a non-polar thermoplastic polymer to form a polymeric lens main body. The method of any one of claims 11 or 12, wherein the polymerizing step comprises polymerizing the polymerizable composition in a contact lens mold assembly having a molding surface formed of a polar thermoplastic polymer to form a polymeric lens body . The method of any one of claims 11 or 12, wherein the contacting step comprises contacting the polymeric lens body with a wash liquor comprising at least one volatile organic solvent.